BRPI0609826A2 - composition suitable for use on stretch films and laminates, stretch film layer, laminate and article made - Google Patents

Abstract

SUITABLE COMPOSITION FOR USE ON FILMS AND ELASTIC LAMINATE, ELASTIC FILM LAYER, LAMINATE AND MANUFACTURED ARTICLE. The present invention relates to polyolefin compositions. In particular, the invention relates to elastic polymeric compositions which can be more easily processed into melt, extrusion lamination or coating lines due to improved resistance to stretch resonance. The compositions of the present invention preferably comprise an elastomeric polyolefin resin and a low density high pressure type resin.

Description

"SUITABLE COMPOSITION FOR USE ON FILMS AND ELASTIC LAMINATE, ELASTIC FILM LAYER, LAMINATE AND ARTICLE MANUFACTURE"

Field of the invention

The present invention relates to co-sealing ethylene / α-olefin multiblock interpolymer compositions for stretch films and laminates with improved stress relaxation. Compositions can often be processed more easily into melt cell lines, coating lines or extrusion lamination due to improved draw resonance resistance.

History and Summary of the Invention

It is often desirable to coat an article, substrate or film to modify properties. An especially desirable coating is that of an elastic film, that is, a film which is capable of being stretched without breaking or substantially returning to its original shape. Thus, the article, substrate or film may be used to form structures that require elasticity.

Elastic films made of elastomeric polymers have found use in laminates. Laminates are conveniently prepared by coating a substrate, such as paper or film, with an elastic layer by extrusion coating. Extrusion coating is a process whereby a polymer or polymer blend is fed into an extruder funnel. In the funnel, the polymer or mixture is fed and passed through a matrix to form a mat. The mat is then extruded onto the substrate via a pressure / cooling cylinder interface, for example, such that the molten mat is compressed onto the substrate. The substrate is cooled through the cooling cylinder and wound in a winder.

Elastic films made of elastomeric polymers have found specific use in laminates, where the substrate is a nonwoven, since the elastic film confers elasticity to nonwoven laminates. Such nonwoven elastic laminate materials have found medical and hygienic use especially in such applications as elastic diaper straps, gymnastic trousers, panty leg purses, feminine hygiene articles, swimming trousers, incontinence clothing, veterinary products, bandages, health care items such as surgeon's lab coats, operating room curtains, sterilized films, cloths, and the like. These materials may find use in other nonwoven applications, including but not limited to filters (gas and liquid), automotive and marine protective covers, home accessories such as bedding, carpet liners, wallcoverings, floor coverings, blinds, coverings, etc. Such elastic films may be incorporated into delaminated designs, such as those described in WO9003464A2 and U.S. Pat. 4,116,892 and 5,156,793. Many different processes are often employed to make single or multilayer stretch films. Such processes may include bubble extrusion or biaxial orientation processes, such as rack drawing techniques. For ease of elasticity, the elastic film is generally employed alone or as the outermost layer in the case of multilayer films.

Elastic films are often employed using molten film processes. In a typical molten film process, the molten polymer is extruded through a die and then the molten film is poured into the decompression / cooling cylinders, where it is rapidly cooled in the cooling cylinder. Especially as production speed increases, a phenomenon known as stretch resonance may occur under specific extrusion conditions, especially when using a nip. Stretch resonance is the term given to periodic fluctuations in machine direction (MD) film thickness that corresponds to periodic variations in transverse (CD) film thickness. Stretch resonance results in film instability that may restrict the productivity of commercial processes . Stretch resonance is known as a specific problem in polyolefin elastomers, especially linear polyolefins. Accordingly, one of the objectives is to reduce or eliminate stretch resonance in film production, particularly in the production of stretch films. This phenomenon was previously described in the scientific literature. Here are some examples:

Silagy, D.J. Neon-Newtonian Fluid Mech., "Stationary and Stability Analysis of the Film Casting Process," pp.563-583, vol.79 (1998).

Silagy, D., "Theoretical & Experimental Analysis of Line Speed Limitations in the Film Casting of Polyethylene", 6th European TAPPI Seminar on Polymers, Films and Coatings, Copenhagen, June 8-9, 1999.

Denn, M., "Instabilities in Polymer Processing", AICHE J. (22), No.2, p.209-236 (March, 1976).

Anturkar, N., "Draw Resonance Film Casting of Viscoelastic Fluids: A Linear Stability Analysis", of Non-Newtonian Fluid Mech., 28, p.287-307 (1998).

Pis-Lopz, M., Multilayer Film Casting of Modified Giesekus Fluids Part 1. Steady State Analysis, "J.Non-Newtonian Fluid Mech., 66 p.71-93 (1996).

Bortner, M., "Dependence of Draw Resonance on Extensional Rheological Properties of LLDPE", SPE 2003 ANTEC.

Smith, Spencer, "Numerical Simulation of Film Castingusing in Updated Lagrangian Finite Element Algorithm" Polymer Engineering and Science, May 2003, vol.43, No. 5, p.1105.

Elastic films made with conventional plastomer and polyolefin elastomer compositions in an extrusion / coating lamination application are often slow or difficult to produce due to stretch resonance or neck-in. Therefore, suitable compositions for elastic or laminated films are desired. which may be produced more easily and having equal or better elasticity.

Examples of processes, manufacturing, and articles suitable for use with the present inventions include, but are not limited to, EP472 942B1, EO0707106B1, US4422 892, US45254 07, US4 72 0415, US4965122, US4981747, US5114781, US5169706, US522 6992, US522 6992 6545, US5514470, WO0 9003258A1, WO0 9003464A2, EP0575508B1, US6605172, US5660214, US3.833.973, US3860 003, US4116892, US5156793, US5696353, US5691035, US5891544, the present invention, laminates, elastic bands.

Elastic films and laminates can easily be produced from compositions of the invention and often have elasticity equal to or better than conventional compositions. Compositions suitable for use in elastic or laminated films comprise at least one ethylene / Î ± -olefin interpolymer, wherein the ethylene / α-olefin interpolymer is:

(a) has a Mw / Mn of about 1,7 to 3,5, at least one melting point, Tm in degrees Celsius, and a density, d, in grams / cubic centimeter, where the numerical values of Tm and d match the ratio:

Tm> - 2002.9 + 4538.5 (d) - 2422.2 (d) 2.

(b) has a Mw / Mn of about 1.7 to about 3.5, defined by a fusion heat, AH in J / g and a delta amount, AT, in degrees Celsius defined as the temperature difference between the DSC peak. highest and highest CRYSTAF, where the numerical values of AT and AH have the following ratios:

AT> -0.1299 (HA) + 62.81 for HA greater than zero and up to 130 J / g,

AT> 48 ° C for AH greater than 130 J / g,

where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 ° C; or

(c) is defined by an elastic recovery, Re, at 300 per cent strain and 1 cycle measured with a compression molded film of the ethylene / α-olefin interpolymer, and has a density, d, in grams / centimeter where the values Re ed numerics satisfy the following relationship when the ethylene / α-olefin interpolymer is substantially free of a cross-linked phase:

Re> 1481 - 1629 (d); or

(d) has a molecular fraction eluting between 40 ° C and 130 ° C when fractionated using TREF, with the fraction having a molar comonomer content at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures. where said comparable random random ethylene interpolymer has the same comonomer (s) and a melt index, density and molar comonomer content (based on total polymer) in the range of 10 per cent of that of the ethylene interpolymers / a -olefin; or

(e) has a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° C, G' (100 ° C), where the ratio of G "(25 ° C) to G "(100 ° C) is about 1: 1 about 9: 1

where the ethylene / α-olefin interpolymer has a density of about 0.85 to about 0.89 g / cc and a melt index (I2) of about 0.5 g / 10 min to about 20 g / 10 min .

Brief Description of Drawings

Figure 1 shows the melting point / density ratio for the polymers of the invention (represented by diamonds) compared to traditional random copolymers (represented by circles) and Ziegler-Natta copolymers (represented by triangles).

Figure 2 shows DSC-CRYSTAF delta graphs with DSC Fusion Enthalpy function for various polymers. The diamonds represent random ethylene / octeno copolymers; squares represent examples of polymer 1-4; triangles represent examples of polymer 5-9; and the circles represent Polymer Examples 10-19. The symbols "X" represent Polymer Examples A * -F *.

Figure 3 shows the effect of density on elastic recovery for non-oriented films made of interpolymers of the invention (represented by squares and circles) and traditional copolymers (represented by triangles which are the Dow AFFINITY® diverse polymers). The squares represent the ethylene / butene polymers of the invention, and the circles represent the ethylene / octene copolymers of the invention.

Figure 4 is a graph of the octene content of fractional ethylene / 1-octene TREF fractional fractions versus fraction TREF elution temperature for the polymer of Example 5 (represented by circles) and comparative polymers E * and F * (represented by the symbols "X"). ") .The lozenges represent the traditional random ethylene / octeno-copolymers.

Figure 5 is a graph of the octene content of fractional ethylene / 1-octene TREF fractionated fractions versus fraction TREF elution temperature for the polymer of Example 5 (curve 1) and for Comparative F (curve 2). The squares represent Example F *; and the triangles represent Example 5.

Figure 6 is a graph of the storage modulus log as a function of temperature for comparative ethylene / 1-octene copolymer (curve 2) and ethylene / propylene copolymer (curve 3) and for two ethylene / 1-octene block copolymers. invention made with different amounts of chain transfer agent (curves 1).

Figure 7 shows a graph of TMA (1mm) versus flexural modulus for some polymers of the invention (represented by diamonds) compared to some known polymers. Triangles represent diverse DOW VERSIFY® polymers; the circles represent random ethylene / styrene diversoscopolymers; and the squares represent the various DowAFFINITY® polymers.

Figure 8 shows the recovery-density behavior ratio of the compositions of the invention compared to traditional random copolymer.

Figure 9 shows the relaxation behavior at 50% deformation after 10 hours at 37 ° C for comparative skin and laminate films of the invention.

Figure 10 shows the relaxation behavior at 75% deformation after 10 hours at 37 ° C for comparative skin and laminate films of the invention.

Detailed Description of the Invention

General Definitions

The following terms will have the meanings assigned to them for the purposes of the present invention:

By "stretch resonance" is meant a cyclolimite corresponding to the periodic constant oscillation in the velocity and cross-sectional area of a cooling process when the perimeter conditions are a fixed velocity at the outlet of an extruder and a fixed velocity in the removal position.

By "neck-in" is meant the reduction in width of a film web as it is extruded from a matrix and will be caused by a combination of bulging effects and surface tension as the material leaves the matrix. The reduced width is measured as the distance between the extruded blanket when it emerges from the matrix minus the extruded blanket width when it is collected. "Polymer" means a polymeric compound prepared by polymerizing monomers, whether of the same or different type. The generic term "polymer" encompasses the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer".

"Interpolymer" means a polymer prepared by polymerizing at least two different types of monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally employed to refer to a polymer prepared from two different monomers) as well as the term "terpolymer" (which is generally used to refer to a prepared polymer of three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.

The term ethylene / of-olefin interpolymer "generally refers to polymers comprising ethylene and an otolefin having 3 or more carbon atoms. Preferably, ethylene comprises most of the molar fraction of the total polymer, ie ethylene comprises at least about 50 mol percent of the total polymer More preferably, ethylene comprises at least about 60 mol percent, at least about 70 mol percent, or at least about 80 mol percent, with the substantial remainder of the total polymer comprising at least another comonomer which is preferably an α-olefin having 3 or more carbon atoms.For many ethylene / octene copolymers, the preferred composition comprises an ethylene content of greater than about 80 mol percent of the total polymer and an octene content of about 10 to 10%. about 15, preferably from about 15 to about 20 mol percent of the total polymer. Ethylene / α-olefin interpolymers do not include those produced in low yields either in a smaller amount or as a by-product of a chemical process. Although ethylene / α-olefin interpolymers may be mixed with one or more polymers, the ethylene / α-olefin interpolymers produced in this way are substantially pure and often comprise a major component of the reaction product of a polymerization process.

Ethylene / α-olefin interpolymers comprise ethylene and one or more polymerizable o-olefin comonomers in polymerised form, characterized by blocks or multiple segments of two or more polymerized monomer units that differ in chemical or physical properties. That is, the ethylene / α-olefin interpolymers are block interpolymers, preferably multiblock interpolymers or copolymers. The terms "interpolymer" and "copolymer" are used in the present invention reciprocally. In some embodiments, the multiblock copolymer may be represented by the following formula:

(AB) n

where n is at least 1, preferably an integer greater than 1, such as 2,3,4,5,10,15,20,30,40,50,60,70,80,90,100 or greater. "A" represents a hard block or segment and "B" represents a soft block or segment. Preferably, As and Bs are linked substantially linearly, as opposed to substantially branched or substantially star-shaped. In other embodiments, blocks A and blocks B are randomly distributed along the polymeric chain. In other words, block copolymers generally do not have a structure as follows:

AAA - AA-BBB - BB

In still other embodiments, the block copolymers generally have a third type of block, which comprises different comonomer (s). In still other embodiments, each block A and block B have substantially randomly distributed monomers or comonomers within the block. In other words, neither oblique A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition, such as the terminal segment, which has a composition substantially different from that of the rest of the block.

Multiblock polymers typically comprise several amounts of "hard" and "soft" segments. "Hard" segments refer to polymerized unit blocks wherein ethylene is present in an amount greater than about 95 weight percent, and preferably greater than about 100 weight percent. 98 weight percent based on the weight of the polymer. In other words, the comonomer content (non-ethylene monomer content) in our hard segments is less than about 5 weight percent, and preferably less than about 2 weight percent, based on the weight of the polymer. In some embodiments, the hard segments comprise all or substantially all ethylene. "Soft" segments, on the other hand, refer to polymerized unit blocks wherein the comonomer content (monomer content other than ethylene) is greater than about 5 weight percent, preferably greater than about 8 weight percent. , greater than about 10 weight percent or about 15 weight percent, based on the weight of the polymer. In some embodiments, the content of soft segment comonomers may be greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent. weight, greater than about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 weight percent.

Soft segments may often be present in a block interpolymer of from about 1 percent by weight to about 99 percent by weight of the total weight of the block interpolymer, preferably from about 5 percent by weight to about 95 percent by weight. about 10 weight percent to about 90 weight percent, from about 15 weight percent to about 85 weight percent, from about 20 weight percent to about 80 weight percent, from about 25 percent by weight about 75 percent by weight, from about 30 percent by weight to about 70 percent by weight, from about 35 percent by weight to about 65 percent by weight, about 40 percent by weight by weight to about 60 weight percent, or from about 45 weight percent to about 55 weight percent of the total weight of the block interpolymer. In contrast, hard segments may be present in similar ranges. The percentage by weight of soft segment and the percentage by weight of durop segment can be calculated based on data obtained from DSC or NMR. Such methods and calculations are described in a Request for

Concomitantly filed U.S. Serial No. (insert where known), Prosecutor Document No. 385063-999558, entitled "Ethylene / ai-Olefin Block Interpolymers", filed March 15, 2006, in the name of Colin LPShan, Lonnie Hazlitt, et .al. Dow Global Technologies, Inc., the disclosure of which is incorporated herein by reference in its entirety. The term "crystalline" when used refers to a polymer having a first order transition or crystalline melting point (Tm) as determined by calorimetry exploratory differential (CSD) or equivalent technique. The term may be used reciprocally with the term "crystalline". The term "amorphous" refers to a polymer without a crystalline melting point as determined by exploratory differential calorimetry (DSC) or equivalent technique.

The term "multiblock copolymer" or "segmented copolymers" refers to a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") which are preferably joined together, that is, a polymer comprising chemically differentiated units which are end-joined. end-point with respect to functionalized ethylenic functionality rather than pendant or grafted form.In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated therein, in the amount of crystallinity, in the size of the crystallite attributable to a polymer of such composition. , type or degree of tacticality (isotactic or syndiotactic), regio-regularity or regio-irregularity, in the amount of branching, including long chain branching or hyper-branching, homogeneity or any physical or chemical property. Multiblock copolymers are characterized by typical distributions of both polydispersity index (PDI or Mw / Mn), block extension distribution, and block number distribution due to the typical copolymer manufacturing process. More specifically, when produced in a continuous process, the polymers desirably have PDIs of 1.7 to 2.9, preferably 1.8 to 2.5, more preferably 1.8 to 2.2, and most preferably 1.8 to 2, 1. When produced in a batch or semi-batch process, the polymers have PDI from 1.0 to 2.9, preferably from 1.3 to 2.5, most preferably from 1.4 to 2.0, and most preferably from 1. , 4 to 1.8.

In the following description, all numbers described in the present invention are approximate values, regardless of whether the word "about" or "approximate" is used with respect to them. They can vary by 1 percent, 2 percent, 5 percent, or sometimes 10 to 20 percent. Whenever a numeric range with a lower limit, RL and an upper limit, Ru, is described, any number falling within the range is specifically described. In particular, the following numbers within the range are specifically described: R = RL + k * (RU-RL), where k is a variable ranging from 1 per cent to 100 per cent with an increment of 1 per cent, ie, k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent ... 50 percent, 51 percent, 52 percent ..., 95 percent, 96 percent, 97 percent, 98 percent, 99 per cent, or 100 per cent. In addition, any numeric range defined by two numbers R, as defined above, is also specifically described.

For purposes of the present invention, a film is generally considered to be "elastic" if it has a permanent deformation of less than 40% as determined according to the following procedure: samples are loaded onto a Sintech mechanical test device adapted with pneumatically activated line contact cables with a separation. 4 inch initial. Then the sample is drawn to 80% strain at 500 mm / min and returned to 0% strain at the same speed. Deformation to a 10 g load by shrinkage was considered to be permanent deformation.

"Density" is tested according to ASTM D792. "Melt index" (12) is determined according to ASTMD1238 using a weight of 2.16kg at 190 ° C for polymers comprising ethylene as the main component in the polymer.

"Melt Flow Rate (MFR)" is determined according to ASTM D1238 using a weight of 2.16 kg at 230 ° C for polymers comprising propylene as a major component in the polymer.

"Molecular Weight Distribution" or MWD is measured by conventional GPC according to the procedure described by Williams, T.; Ward, I. M. Journal of Polymer Science, Polymer Letters Edition (1968), 6 (9), 621-624.

Coefficient B is 1. Coefficient A is 0.4316.The term "high pressure low density type resin" is defined as meaning that the polymer is partially fully homopolymerized or copolymerized in a autoclave or tubular reactor at pressures above 14,500 psi (100 MPa ) with the use of free radical initiators such as peroxides (see for example US 4,599,392, incorporated herein by reference) and includes "LDPE" which may also be referred to as "high pressure ethylene polymer" or "highly deified polyethylene". The CDF of these materials is greater than about 0.02.

The term "high pressure low density type resin" also includes polypropylenamidified materials (both homopolymer and copolymer). Paraffins of the present invention, "polypropylenamidified materials" mean the type polypropylenamidified materials described in WO2003 / 082971, incorporated herein by reference in their entirety.

Ethylene / α-Olefin Interpolymers

Ethylene / ce-olefin interpolymers used in the embodiments of the invention (also called "inventive interpolymer" or "inventive polymer") comprise ethylene and one or more α-olefinacopolymerizable comonomers in polymerized form, characterized by blocks or multiple segments of two or more more polymerized monomer units differing in chemical or physical properties (block interpolymer), preferably a multiblock copolymer. Ethylene / olefin interpolymers are characterized by one or more of the aspects described below. In one aspect, the ethylene / α-olefin interpolymers used in the embodiments of the invention have a MW / Mn of from about 1.7 to about 3.5. , and at least one melting point, Tm, in degrees Celsius, and density, d, in grams / cubic centimeter, where the numerical values of the variables correspond to the following relationship:

Tm> -2.002.9 + 453 8.5 (d) - 2422.2 (d) 2, preferably

Tm> 62 88.1 + 13141 (d) - 672 0.3 (d) 2, and more preferably

Tm> 858.91 - 1825.3 (d) + 1112.8 (d) 2.

Such a melting point to density ratio is illustrated in Figure 1. Unlike traditional random ethylene / α-olefin copolymers whose melting points decrease with decreasing densities, the interpolymers of the invention (represented by diamonds) exhibit substantially density-independent melting points, especially when the density is between about 0.87 g / cc to about 0.95 g / cc. For example, the melting point of such polymers is in the range of about 110 ° C to about 130 ° C, when the density ranges from 0.875 g / cc to 0.945 g / cc. In some embodiments, the melting point of such polymers is in the range of about 115 ° C to about 125 ° C, when the density ranges from 0.875 g / cc to about 0.945 g / cc.

In another aspect, the ethylene / α-olefin interpolymers comprise, in the polymerized form, ethylene and one or more olefins and are characterized by an AT, in degrees Celsius, defined as the temperature for the highest peak Exploratory Differential Calorimetry (" DSC ") minus the temperature for the Crystallization Analysis Fractionation peak (" CRYSTAF11) and a fusion heat at J / g, AT and AH satisfy the following ratios:

AT> -0.1299 (AH) + 62.81, and preferably

AT> 0.1299 (AH) + 64.38, and more preferably,

AT> 0.1299 (AH) + 65.95,

for HA up to 130 J / g. In addition, AT is equal to or greater than 48 ° C for HA greater than 130 J / g. The CRYSTAF peak is determined using at least 5 percent of the cumulative polymer (ie the peak should represent at least 5 percent of the cumulative polymer) and if less than 5 percent of the polymer has a identifiable CRYSTAF peak, then the CRYSTAF temperature is 3 0 ° C, eAH is the numerical value of the fusion heat in J / g. Most preferably, the highest CRYSTAF peak contains at least 10 percent of the cumulative polymer. Figure 2 shows the plotted data for the polymers of the invention as well as the comparative examples. The integrated peak areas and peak temperatures are calculated using the computer design program provided by the instrument manufacturer. The diagonal line shown for comparative random octeno ethylene polymers corresponds to the equation AT = -0.1299 (AH) +62.81.

In yet another aspect, the ethylene / α-olefin interpolymers have a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using Elution Fraction and Temperature Elevation ("TREF"), characterized by the fact that said fraction has a fraction. molar higher comonomer content, preferably at least 5 percent higher, more preferably at least 10 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, with the comparable random ethylene interpolymer containing the same (s). ) comonomer (s) and has a melt index, density and molar comonomer content (based on total polymer) in the range of 10 percent of the block dointerpolymer. Preferably, the Mw / Mn of the comparable interpolymer is also in the 10 percent range of the block interpolymer and / or the comparable interpolymer has the total comonomer content in the range of 10 percent by weight of that of the block interpolymer.

In yet another aspect, the ethylene / olefin interpolymers are characterized by elastic recovery, Re, in percent to 300 percent strain, and 1 cycle measured on a compression molded film of an ethylene / α-olefin interpolimer, and have a density, d, in grams / cubic centimeter, where the numerical values of Re ed satisfy the following relationship when the ethylene / α-olefin interpolymer is substantially free of a cross-linked phase:

Re> 1481-1629 (d); and preferably

Re> 1491-1629 (d); and more preferably

Re> 1501-1629 (d); and even more preferably

Re> 1511-1629 (d).

Figure 3 shows the effect of density on elastic recovery for non-oriented films made with certain inventive interpolymers and traditional random copolymers. For the same density, inventive interpolymers have substantially higher elastic recoveries.

In some embodiments, the ethylene / olefin interpolymers have a tensile strength above 10 MPa, preferably a tensile strength> 11MPa, more preferably a tensile strength> 13MPa and / or a tensile elongation of at least 600 percent, more preferably at least 700 percent, highly preferably at least 800 percent, and most preferably at least 900 percent at a crosshead separation rate of 11 cm / minute. In other embodiments, the ethylene / interpolymers α-olefin have (1) a storage modulus ratio, G "(25 ° C) / G '(100 ° C), from 1 to 50, preferably from 1 to 20, more preferably from 1 to 10; and / or (2) a permanent compression strain at 70 ° C below 80 per cent, preferably below 70 per cent, especially below 60 per cent, below 50 per cent, or below 40 per cent. per cent to a permanent deformation at 0 per cent compression.

In still other embodiments, the ethylene / α-olefin interpolymers have a permanent compression strain at 70 ° C below 80 percent, below 70 percent, below 60 percent, or below 50 percent. Preferably, the permanent deformation at 70 ° C compression of the interpolymers is less than 40 percent, less than 30 percent, less than 20 percent, and can be up to about 0 percent.

In some embodiments, the ethylene / ce-olefin interpolymers have a melt heat of less than 85 J / 9 and / or a pellet block resistance of 100 pounds per square foot (4800 Pa), preferably 50 pounds or less / square foot (2400 Pa), especially 5 pounds / square foot or less (240 Pa) and as low as 0 pounds / square foot (0 Pa). In other embodiments, the ethylene / o: -olefin interpolymers comprise , in the polymerized form, at least 50 mol percent ethylene and a permanent compression strain at 70 ° C below 80 per cent, preferably below 70 per cent or below 60 per cent, most preferably below 40 to 50 per cent. and even close to zero percent.

In some embodiments, multibloc copolymers have a PDI that fits a Schultz-Flory distribution rather than a Poisson distribution. The copolymers are further characterized by having both a polydisperse block distribution and a polydisperse distribution of block sizes and having a more likely distribution of block extensions. Multi-preferred copolymers are those containing 4 or more segment blocks, including terminal blocks. More preferably, the copolymers include at least 5, 10, or 20 blocks or segments including terminal blocks. Comonomer content may be measured using any appropriate technique, with nuclear magnetic resonance ("NMR") based techniques being preferred. In addition, for polymers or polymer mixtures having relatively broad TREF curves, the polymer is desirably first fractionated using TREF in fractions, each having an eluted temperature range of 10 ° C or less. Deeply, each eluted fraction has a collection temperature window of 10 ° C or less. Using such a technique, said block interpolymers have at least one talfaction having a higher molar comonomer content than the corresponding fraction of the comparable interpolymer. In another aspect, the inventive polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymer comonomers. polymerizable form, characterized by multiple blocks (i.e. at least two blocks), or segments of two or more polymerized demonomer units that differ in chemical or physical properties (block interpolymer), most preferably a multiblock copolymer, said interpolator in block having a peak (but not just a molecular fraction) that elutes between 40 ° C and 130 ° C (but without collecting and / or isolating individual fractions), characterized in that said peak has a deconomer content measured by infrared spectroscopy when expanded using if a maximum width area calculation / half maximum (FWHM), has a higher average molar comonomer content, preferably at least 5 per cent higher, more preferably at least 10 per cent higher than the random ethylene interpolymer peak comparable to the same elution temperature and expanded using a calculation. maximum width / half maximum (FWHM) area where said comparable random ethylene interpolymer has the same comonomer (s) and a melt index, density, molar comonomer eteor (based on total polymer) in the range of 10 percent percent of the block interpolymer.

Preferably, the Mw / Mn of the comparable interpolymer is also in the range of 10 per cent of the block interpolymer and / or the comparable interpolymer has a total deconomer content in the range of 10 per cent by weight of the block interpolymer. The maximum width / half maximum (FWHM) calculation is based on the ratio of methyl to methylene response area [CH3 / CH2] of the infrared detector ATREF, with the highest peak being identified from the baseline, then the FWHM area being determined. . For a distribution measured using an ATREF peak, the FWHM area is defined as the area under the curve between Tx and T2, where T ± and T2 are determined points to the left and right of the ATREF peak by dividing the peak height by two, and then drawing a horizontal line to the baseline, which intersects the left and right portions of the ATREF curve. A calibration curve for the comonomer content is made using random ethylene / α-olefin copolymers by plotting the NMRversus comonomer content of the FWHM area ratio of the TREF peak. For this infrared method, the calibration curve is generated for the same type of comonomer of interest. The TREF peak deconomer content of the inventive polymer can be determined by reference to this calibration curve using its TREF peak methylene [CH3 / CH2] FWHM area ratio.

Comonomer content may be measured using any appropriate technique, with techniques based on nuclear magnetic resonance spectroscopy (NMR) being preferred. Using this technique, said block interpolymers have a higher molar comonomer content than a comparable matched interpolymers.

Preferably, for ethylene and 1-octene interpolymers, the block interpolymer has a TREF fraction deconomer content eluting between 40 and 140 ° C increased by the amount (-0.2013) T + 20.7, more preferably higher or lower. equal to the quantity (-0.2013) T + 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction being compared, measured in ° C.

Figure 4 graphically depicts one embodiment of the ethylene and 1-octene block interpolymers where a graph of comonomer content versus TREF elution temperature for various comparable ethylene / 1-octene interpolymers (random copolymers) is fitted to a line representing (-0.2013 ) T + 20.07 (lineal). The line for equation (-0,2013) T + 21,07 is represented by a dotted line. Comonomer contents are also shown for the various interpolymers of ethylene / 1-octene block fractions of the invention (multiblock copolymers). All block interpolymer fractions have a significantly higher 1-octene content than any line at equivalent elution temperatures. This result is characteristic of the interpolymer of the invention and is believed to be due to the presence of differentiated blocks, both crystalline and amorphous in nature.

Figure 5 graphically shows the TREF curve and polymer fraction comonomer contents for Example 5 and Comparative F to be discussed below. The peak eluting from 40 to 130 ° C, preferably from 60 ° C to 95 ° C for both polymers is fractionated into three parts, each part eluting in a temperature range below 10 ° C. The actual data for Example 5 is represented by triangles. One skilled in the art may appreciate that an appropriate calibration curve may be constructed for interpolymers containing different comonomers and a line used as a comparison adjusted to the TREF values of comparative interpolymers of the same monomers, preferably prepared random copolymers using metallocene or other homogeneous catalyst composition. The interpolymers of the invention are characterized by a molar content greater than the value determined from the calibration curve at the same TREF elution temperature, preferably at least 5 percent higher, more preferably at least 10 percent higher.

In addition to the above aspects and properties, the polymers of the invention may be characterized by one or more additional features. In one aspect, the polymer of the invention is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by blocks or multiple segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), most preferably a multiblock copolymer, said block interpolymer having a molecular fraction eluting between 40 ° C and 130 ° C, when fractionated using TREF increments, characterized in that said fraction has a higher molar comonomer content, preferably at least 5 per cent. higher, more preferably at least 10, 15, 20 or 25 per cent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, said comparable random ethylene interpolymer comprising the same comonomer (s), preferably it is the same comonomer (s), and a melt index, density, and molar decomonomer content (based on total polymer) in the range of 10 percent of the Preferably, the Mw / Mn of the comparable interpolymer is also in the range of 10 per cent of that of the block interpolymer and / or the comparable interpolymer has a total deconomer content in the range of 10 per cent by weight of the block interintermer.

Preferably, the above interpolymers are ethylene interpolymers and at least one α-olefin, especially interpolymers having a total polymer density of about 0.855 to about 0.935 g / cm3, and more especially for polymers having more than about 1 mole percent. As a comonomer, the block interpolymer has a TREF fraction comonomer content eluting between 40 and 130 ° C greater than or equal to the amount (-0.1356) T + 13.89, more preferably greater than or equal to the amount (-0.1356) T + 14.93, and most preferably greater than or equal to the amount (-0.2013) T + 21.07, where T is the numerical value of the peak elution temperature of the compared TREF fraction, measured in ° C.

Preferably, for the above ethylene and interpolymers of at least one alpha olefin especially those interpolymers having a total polymer density of about 0.855 to about 0.935 g / cm3, and more especially for polymers having more than 1mole percent comonomer, the bloc interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 ° C greater than or equal to the amount (-0.2013) T + 20.07), more preferably greater than or equal to the amount (-0.2013) T + 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction being compared, measured in ° C.

In still another aspect, the inventive polymer is an olefinic interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomeric units differing in chemical or physical properties (block interpolimer), most preferably a copolymer. multiblock, said block interpolymer having a molecular fraction which elutes between 40 ° C and 130 ° C when fractionated using TREF increments, characterized in that all fraction with a comonomer content of at least about 6 moles has a point melting greater than about 100 ° C. For fractions having a deconomer content of about 3 mol percent to about 6 mol percent, every fraction has a DSC melting point of about 110 ° C or higher. More preferably, said polymer fractions, having at least 1 mol percent deconomer, have a DSC melting point that corresponds to the equation:

Tm> (-5.5926) (mol percent comonomer in fraction) +135.90

In yet another aspect, the inventive polymer is an olefinic interpolymer preferably comprising ethylene and one or more copolymerizable comonomers in the polymerized form, characterized by multiple blocks or segments of two or more polymerized monomeric units differing in chemical or physical properties (block interpolymer), most preferably a copolymer. multiblock, said block interpolymer having a molecular fraction eluting between 40 ° C and 130 ° C, when fractionated using TREF increments, characterized in that all fraction having an ATREF elution temperature has increased to about 76 ° C, has a fusion enthalpy (fusion heat) measured by DSC, corresponding to the equation:

Melting Heat (J / g) <(3.1718) (Celsius TREF elution temperature) - 136.58.

The block interpolymers of the invention have a molecular fraction eluting between 40 ° C and 130 ° C when fractionated using TREF increments, characterized in that any fraction having an elution temperature of TREF between 40 ° C and less than about 76 ° C C, has a fusion mental (fusion heat) measured by DSC, corresponding to the equation:

Melting Heat (J / g) s (1.1312) (Celsius TREF elution temperature) - 22.97.

ATREF Peak Comonomer Composition Infrared Detector Measurement

The ATREF peak comonomer composition can be measured using an infrared detector from Polymer Char, Valencia, Spain (http://www.polymerchar.com/).

The detector's "compositing mode" is equipped with a metering sensor (CH2) and compositing sensor (CH3) for fixed narrow-band infrared filters in the 2800-3000 cm region. "1 The metering sensor detects methylene carbon ( CH2) in the polymer (which refers directly to the polymer concentration in solution) while the composition sensor detects the methyl (CH3) dopolymer groups.The mathematical ratio of the composition signal (CH3) divided by the measurement signal (CH2) is sensitive to the same. The polymer comonomer solution measured in solution and its response is calibrated to known ethylene-alpha olefin copolymer standards.

The detector when used with an ATREF instrument provides a response to the concentration signal (CH2) as a decomposition (CH3) of the eluted polymer during the ATREF process. A specific polymer calibration can be created by measuring the area ratio of CH3 to CH2 for polymers with known comonomer content (preferably measured by NMR). The deconomer content of an ATREF peak of a polymer can be assessed by applying the area-related reference calibration for the individual CH3 and CH2 response (ie, the CH3 / CH2 area ratio versus the deconomer content).

Peak area can be calculated using a maximum width / half maximum (FWHM) calculation after applying appropriate reference lines to integrate individual TREF chromatogram signal responses. The maximum width / half maximum calculation is based on the methyl to methylene response area [CH3 / CH2] of the ATREF infrared detector, where the highest peak is identified from the baseline, and then the FWHM area is determined. For a distribution using an ATREF peak, the FWHM area is defined as the area under the curve between TI and T2, where TI and T2 are determined points to the left and right of the ATREF peak, dividing the peak height by two, and then plotting -a horizontal line to a base line, which intersects the left and right portions of the ATREF curve. The application of infrared spectroscopy to measure polymer comonomer ion in this ATREF-infrared method is in principle similar to that of the GPC / FTIR systems, as described in the following references: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley; "Development of gel-permeation chromatography-Fouriertransform infrared spectroscopy for characterization of ethylene-based polyolef in copolymers11. PolymericMaterials Science and Engineering (1991), 65, 98-100; eDeslauriers, PJ; Rohlfing, DC, Shieh, ET; "Quantifying short chain branching microstructures inethylene-1-olefin copolymers using size exclusion chromatography and Fourier transform infraredspectroscopy (SEC-FTIR)", Polymer (2002), 43, 59-170, both incorporated herein by reference in their In other embodiments, the inventive ethylene / o-olefin interpolymer is characterized by a mean block index, ABI, greater than zero and up to about 1.0 and a molecular weight distribution, Mw / Mn, greater than about 1. / 3. The mean block index, ABI, is the weight average of the block index ("BI11) for each of the fractions obtained on preparatory TREF from 20 ° C to 110 ° C with an increment of 5 ° C:

<formula> formula see original document page 27 </formula>

where Bli is the block index for the ith fraction of the ethylene / o-olefin interpolymer of the invention obtained in preparatory TREF, and wi is the weight percentage of the fraction.

For each polymer fraction, BI is defined by one of the following equations (both giving the same BI value):

<formula> formula see original document page 27 </formula>

where Tx is the elution temperature TREF for the ith fraction (preferably expressed in Kelvin), Px is the ethylene molar fraction for the ith fraction, which may be measured by NMR or IR as described above. Pab is the ethylene molar fraction of the ethylene / C-olefinatotal interpolymer (before fractionation), which may also be measured by NMR or IR. TA and Pa are the TREF elution temperature and the ethylene molar fraction for pure "hard segments" (which refer to the crystalline segments of the interpolymer). As a first order approximation, TA and PA values are adjusted to those for high density polyethylene homopolymer if actual values for the "hard segments" are not available. For the calculations made here, TA is 372 ° K, PA is 1.

TAB is the ATREF temperature for a random copolymer of the same composition and having a ethylene molar fraction of Pab-Iab can be calculated based on the following equation:

<formula> formula see original document page 27 </formula> where ae (3 are two constants that can be determined by calibration using known random ethylene polymers. It should be noted that ae (3 may vary from instrument to instrument). It is necessary to create a proper calibration curve with the polymeric composition of interest and also in a similar molecular weight range as fractions. There is a slight molecular weight effect. If the calibration curve is obtained from similar molecular weight ranges, such an effect would be essentially negligible. In some embodiments, random ethylene copolymers satisfy the following interrelation:

Ln P = -237.83 / TAtref + 0.639

TXo is the ATREF temperature for a random copolymer of the same composition and having a molar fraction of ethylene Px-TXo can be calculated from LnPx = ce / TX0 + j8- Conversely, PXo is the ethylene molar fraction for a random composition of the same composition and having an ATREF temperature of Tx, which may be calculated from Ln Pxo = qi / Tx + jS.

Once the block index (BI) is obtained for each preparatory TREF fraction, the weight average block index, ABI, for the total polymer can be calculated. In some embodiments, the ABI is greater than zero, but less than about 0.3 or about 0.1 to about 0.3. In other embodiments, the ABI is greater than about 0.3 and even about 1.0. Preferably, the ABI should be in the range from about 0.4 to about 0.7, from about 0.5 to about 0.7, or from about 0.6 to about 0.9. In some embodiments, ABI is in the range of from about 0.3 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7 of about 0. 0.3 to about 0.6, about 0.3 to about 0.5, or about 0.3 to about 0.4. In other embodiments, the ABI is in the range of about 0.4 to about 0.1, about 0.5 to about 1.0, or about 0.6 to about 1.0, about 0. About 1.0, from about 0.8 to about 1.0, or about 0.9 to about 1.0.

Another feature of the ethylene / olefin interpolymers of the invention is that the ethylene / α-olefin interpolymers of the invention comprise at least one polymer fraction which can be obtained by TREF preparation, the fraction having a block index greater than about 0.1 and up to about 1.0, and a molecular weight distribution, Mw / Mn, greater than about 1.3. In some embodiments, the polymer fraction has a block index of greater than about 0.6 and is up to about 1.0, greater than about 0.7 and up to about 1.0, greater than about 0.8 and up to about 1.0, greater than about 0.9 and up to about 1.0. In other embodiments, the polymer fraction has a block index greater than about 0.1 and up to about 1.0, greater than about 0.2, and up to about 1.0, greater than about 0.3 and about 0.5. to about 1.0, greater than about 0.4, and up to about 1.0, or greater than about 0.4, and up to about 1.0. In still other embodiments, the polymer fraction has a block index of greater than about 0.1, and up to about 0.5, greater than about 0.2, and up to about 0.5, greater than about 0.3. and up to about 0.5, or greater than about 0.4 and up to about 0.5. In still other embodiments, the polymer fraction has a block index of greater than about 0.2 and up to about 0.9, greater than about 0.3 and up to about 0.8, greater than about 0.4. and up to about 0.7, or greater than about 0.5 and up to about 0.6.

For ethylene and α-olefin copolymers, the inventive polymers preferably have (1) a PDI of at least 1.3, more preferably at least 1.5, at least 1.7, or at least 2.0, and most preferably. by minus 2.6 to a maximum value of 5.0, more preferably to a maximum value of 3.5, and especially to a maximum of 2.7; (2) a fusion heat of 80 J / g or less; (3) an ethylene content of at least 50 weight percent; (4) a glass transition temperature, Tg / below -25 ° C, more preferably below -30 ° C / and / or (5) one and only one Tm. In addition, the polymers of the invention may have, either alone or in combination with any other properties described herein, a storage module, G ", such that the log (G") is greater than or equal to 400kPa, preferably greater than or equal to 1.0 MPa, at a temperature of 100 ° C. . In addition, the inventive polymers have a relatively flat storage modulus as a temperature function in the range of 0 to 100 ° C (shown in Figure 6) which is characteristic of block polymers, and previously known for an olefinic polymer, especially an ethylene copolymer and a or more aliphatic C 3-8 α-olefins. (By "relatively flat" in this context it is meant that the log G '(in Pascais) is reduced to less than an order of magnitude between 50 and 100 ° C, preferably between 0 and 100 ° C).

The interpolymers of the invention may be further characterized by a thermomechanical penetration depth of 1 mm at a temperature of at least 90 ° C as well as a flexural modulus of 3 kpsi (20MPa) to 13 kpsi (90 MPa). Alternatively, the interpolymers of the invention may have a thermomechanical analytical depth of penetration of 1 mm at a temperature of at least 104 ° C, as well as a deflection modulus of at least 3 kpsi (20 MPa). They may be characterized as having an abrasion resistance (or volume loss) of less than 90 mm 3. Figure 7 shows the TMA (1 mm) versus flexural modulus for the inventive polymers compared to other known polymers. heat-resistance-resistance significantly better than other polymers.

Additionally, the ethylene / cv-olefin interpolymers may have a melt index, I 2 / from 0.01 to 2000 g / 10 minutes, preferably from 0.01 to 1000 g / 10 minutes, more preferably from 0.01 to 500 g / 10 minutes, especially from 0.01 to 100 g / 10 minutes. In certain embodiments, the ethylene / α-olefin interpolymers have a melt index, I2, of 0.01 to 10 g / 10 minutes, 0.5 to 50 g / 10 minutes, 1 to 30 g / 10 minutes, 1 to 6 g / 10 minutes, or 0.3 to 10 g / 10 minutes. In certain embodiments, the melt index for ethylene / α-olefin polymers is 1g / 10 minutes, 3g / 10mins or 5g / 10mins.

The polymers may have molecular weights, Mw, del.100 g / mole to 5,000,000 g / mole, preferably deloOg / mole to 1,000,000, more preferably from 10,000g / mole to 500,000 g / mole, and especially 10,000 g / mole. mole 300,000 g / mole. The density of the polymers of the invention may be from 0.80 to 0.99 g / cm3 and preferably to ethylene-containing polymers from 0.85 g / cm3 to 0.97 g / cm3. In certain embodiments, the density of the ethylene / α-olefin polymers ranges from 0.860 to 0.925 g / cm3 or 0.867 to 0.910 g / cm3.

The process for making the polymers has been described in patent applications: U.S. Provisional Application No. 60 / 553,906, filed March 17, 2004; US Provisional Application No. 60 / 662,937, filed March 17, 2005; U.S. Provisional Application No.60 / 662,939, filed March 17, 2005; US Provisional Application No. 60/5662 938, filed March 17, 2005; PCT Application No. PCT / US2005 / 008916, filed March 17, 2005; PCT Application No.PCT / US2005 / 008915, filed March 17, 2005; e PCT Application No. PCT / US2005 / 008917, filed March 17, 2005, all incorporated herein by reference in their entirety. For example, such a method comprises contacting ethylene and optionally one or more addition-polymerizable monomers other than ethylene under addition polymerization conditions with a catalyst composition comprising: the reaction mixture or product resulting from the combination of:

(A) a first olefin polymerization catalyst having a high comonomer incorporation index,

(B) a second olefin polymerization catalyst having a comonomer incorporation index of less than 90 percent, preferably less than 50 percent, more preferably less than 5 percent of the catalyst comonomer incorporation index (A), and

(c) a chain transfer agent.

Representative catalysts and transfer agent decadeia are as follows:

Catalyst (Al) is dimethyl [N- (2,6-di (1-methylethyl) phenyl) starch) (2-isopropylphenyl) (α-naphthalen-2-diyl (6-pyridin-2-diyl) methane)] hafnium , prepared in accordance with the teachings of WO 03/40195, 2003US0204017, USSN10 / 429.024, filed May 2, 2003, and WO04 / 24740.

<formula> formula see original document page 32 </formula>

Catalyst (A2) is dimethyl [N- (2,6-di (1-methylethyl) phenyl) starch) (2-methylphenyl) (1,2-phenylene (6-pyridin-2-diyl) methane)] hafnium prepared according to the teachings of WO 03/40195, 2003US0204017, USSN10 / 429.024, filed May 2, 2003, and WO04 / 24740.

<formula> formula see original document page 32 </formula> Catalyst (A3) is dibenzyl bis [N, N "'- (2,4,6-tri (methylphenyl) starch) ethylenediamine] hafnium.

<formula> formula see original document page 33 </formula>

Catalyst (A4) is dibenzyl bis (2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) cyclohexane-1,2-diyl zirconium (IV), prepared substantially in accordance with the teachings of US-A-2004/0010103.

<formula> formula see original document page 33 </formula>

Catalyst (B1) is dibenzyl 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (1-methylethyl) imino) methyl) (2-oxoyl) zirconium

<formula> formula see original document page 33 </formula>

Catalyst (B2) is dibenzyl 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (2-methylcyclohexyl) imino) methyl) (2-oxoyl) zirconium <formula> formula see original document page 34 </formula>

(t-butylamido) dimethyl (3-N-pyrrolyl-1,2,3,3a, 7a, β-inden-1-yl) silanititan substantially prepared in accordance with the teachings of USP 6,268,444;

<formula> formula see original document page 34 </formula>

(C2) catalyst is dimethylmethylphenyl) (2-methyl-1,2,3,3a, 7a, yl) silanititanium prepared substantially according to the teachings of US-A-2003/004286;

<formula> formula see original document page 34 </formula>

Catalyst (C3) is dimethyl (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 8a, 77-s-indacen-1-yl) silanititanium prepared substantially according to the teachings of US-A-2003/004286;

<formula> formula see original document page 34 </formula> Catalyst (D1) is Sigma-Aldrich's debis (dimethyldisiloxane) (inden-1-yl) zirconium dichloride:

<formula> formula see original document page 35 </formula>

Transfer Agents

The transfer agents employed include diethylzinc, di (i-butyl) zinc, di (n-hexyl) zinc, triethylaluminum, trioctylaluminum, triethylgalium, i-butylaluminylbis (dimethyl (t-butyl) siloxane), i-butylaluminylbis (di (trimethylsilyl) ) amide), n-octylaluminum di (pyridine-2-methoxide), bis (n-octadecyl) i-butylaluminum, bis (di (n-pentyl) amide of o-butylaluminum, bis (2,6-di-t- n-octyl aluminum butylphenoxide, n-octyl aluminum di (ethyl (1-naphthyl) amide), bis (2,3,6,7-dibenzo-1-azacycloheptanoamide), ethyl (bis 2,3,6,7- n-octyl aluminum dibenzo-1-azacycloheptanoamide, n-octyl aluminum bis (dimethyl (t-butyl) siloxide, ethyl zinc (2,6-diphenylphenoxide), and ethyl tinc (t-butoxide) deethylzinc.

Preferably, the aforesaid process takes the form of a continuous solution process to form block copolymers, especially multiblock copolymers, preferably multiblocolinear copolymers of two or more monomers, more especially ethylene and a C 3-20 olefin or cycloolefin, and the most especially ethylene and one a -olefin C4_2o using multiple catalysts that are unable to interconvert. That is, the catalysts are chemically distinct. Under continuous solution polymerization conditions, the process is ideally suited for polymerization of monomer mixtures at high monomer conversions. Under such polymerization conditions, the transfer of the decade transfer agent to the catalyst becomes advantageous compared to chain growth, and multiblock copolymers, especially multiblocolinear copolymers, are formed with high efficiency. The interpolymers of the invention can be differentiated Conventional random copolymers, physical polymer mixtures, and bloc-prepared copolymers by sequential monomer addition, fluxionary catalysts, anionic or cationic living polymerization techniques. In particular, if compared to the common random copolymer of the same monomers and demonomer content with crystallinity or equivalent modulus, the interpolymers of the invention have better (higher) thermal resistance when measured by melting point, higher TMA penetration temperature, high temperature tensile strength. higher temperature, and / or higher torsion storage module as determined by dynamic mechanical analysis. Compared to a random copolymer containing the same monomers and monomer content, the inventive interpolymers have permanent deformation at lower compression, particularly at elevated temperatures. , lower stress relaxation, higher drag resistance, higher breaking strength, higher blocking resistance, faster installation due to higher crystallization (solidification) temperature, higher recovery (special temperatures), better abrasion resistance, greater melt strength, and better oil and charge acceptance. The interpolymers of the invention also exhibit an unprecedented ratio of crystallization and branch distribution. That is, the interpolymers of the invention have a relatively large difference between the highest depot temperature measured using CRYSTAF and DSC as melt heat function, especially compared to random copolymers containing the same monomer level monomers or physical mixtures of polymers, such as a mixture of a high density polymer and a lower density polymer , at an equivalent total density. This unpublished feature of the interpolymers of the invention is believed to be due to the unpublished distribution of the block comonomer in the main polymer chain. In particular, the interpolymers of the invention may comprise alternate blocks of different comonomer content (including homopolymer blocks). The interpolymers of the invention also comprise a block number and / or block size distribution of the different density and comonomer content, which is a Schultz-Flory distribution type. In addition, the interpolymers of the invention also have an unprecedented peak melting point and crystallization temperature profile that is substantially independent of polymer density, modulus and morphology. In a preferred embodiment, the microcrystalline order of the polymers demonstrates characteristic spherulites and blades that are distinguishable from random or block copolymers, even at PDI values that are less than 1.7, even less than 1.5, even less than 1.3.

In addition, the interpolymers of the invention may be prepared using techniques to influence the degree of block formation. That is, the amount of the deconomer and the length of each polymer block or segment can be changed by controlling the ratio and type of catalysts and the transfer agent as well as the polymerization temperature and other polymerization variables. A surprising benefit of this phenomenon is the discovery that as the degree of block formation is increased, the optical properties, breaking strength and temperature recovery properties are improved. In particular, opacity decreases, while the properties of transparency, tear strength and high temperature recovery increase as the average number of nopolymer blocks increases. By selecting the translational agents and catalyst combinations with desired chain transfer capability (high rates transferred with low levels of chain termination) other forms of polymer termination are efficiently suppressed. Accordingly, little or no β-hydride elimination is observed in the polymerization of ethylene / Î ± -olefin comonomer mixtures according to embodiments of the invention and the resulting crystalline blocks are highly or substantially completely linear, having little or no long chain modification.

Polymers with high crystalline chain ends may be selectively prepared according to embodiments of the invention. In elastomer applications, reducing the relative amount of amorphous block-terminated polymer polymer reduces the effect of intermolecular dilution in crystalline regions. This result can be achieved by selecting decadeia transfer agents and catalysts that have an appropriate response to hydrogen or other decadeia terminator agents. Specifically, if the catalyst that produces highly crystalline polymer is more susceptible to chain termination (such as by using hydrogen) than the catalyst responsible for producing less crystalline polymer segment (such as through greater comonomer incorporation, regio-error, or polymer formation). highly crystalline segmentosphere will preferably populate the terminal portions of the polymer. Not only are the resulting terminating groups crystalline, but upon termination, the highly crystalline polymer which forms the catalyst olocal becomes available again to initiate polymer formation. The initially formed polymer is therefore another highly crystalline polymeric segment. Accordingly, both ends of the resulting multiblock polymer are preferably highly crystalline.

The ethylene / olefin interpolymers used in the embodiments of the invention are preferably ethylene interpolymers of at least one C3 -C20 α-olefin. Ethylene copolymers and a C3 -C20 α-olefin are especially preferred. Interpolymers may further comprise C4 -C18 diolefin and / or alkenylbenzene.

Suitable unsaturated comonomers useful for ethylene polymerization include, for example, ethylenically unsaturated monomers, conjugated or unconjugated dienes, polyenes, alkenylbenzenes, etc. Examples of such comonomers include C3 -C20 α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decenoe similar. 1-butene and 1-octene are especially preferred. Other monomers include styrene, alkyl substituted styrenes, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, enaphthenics (eg, cyclopentene, cyclohexene, eccycloocten).

Although ethylene / α-olefin interpolymers are preferred polymers, other ethylene / α-olefin polymers may also be used. Olefins used in the present invention refer to a family of unsaturated hydrocarbon-based compounds with at least one carbon-carbon double bond. Depending on the selection of catalysts, any olefin may be used in embodiments of the invention. Preferably olefins are C3 -C20 aliphatic and aromatic compounds containing vinyl unsaturation, as well as compostoscics such as cyclobutene, cyclopentene, dicyclopentadiene and norbornene, including, but not limited to, 5 and 6-substituted norbornene with hydrocarbyl or C1-4 hydrocarbyl groups. -C20 • Also included are mixtures of such olefins as well as mixtures of such olefins with C4-C40 diolefin compounds.

Examples of olefinic monomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-dodecene, 1-tetradecene , 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene , vinylcyclohexane, norbornadiene, ethylidene, norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, but not limited to C4-C20 / di 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene 1,7-octadiene, 1,9-decadiene, other C 4 -C 20 otolefins and the like. In certain embodiments, aceolefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or a combination thereof. While any vinyl group-containing hydrocarbon may potentially be used in the embodiments of the invention, the cost and ability to conveniently remove unreacted monomeron from the resulting polymer may become more problematic as the molecular weight of the monomer becomes too high.

The polymerization processes described herein are quite suitable for the production of olefinic polymers comprising aromatic monovinylidene monomers including styrene, o-methyl styrene, p-methyl styrene, t-butylstyrene, and the like. In particular, interpolymers comprising ethylene and styrene may be prepared by following the teachings of the present invention. Optionally, copolymers comprising ethylene, styrene and a C3 -C20 alpha olefin / optionally comprising a C4 -C20 diene with improved properties may be prepared.

Suitable unconjugated diene monomers may be straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms. Examples of suitable unconjugated dienes include, but are not limited to, linear acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1 6-octadiene; 3,7-dimethyl-1,7-octadiene and

mixed isomers of dihydromyricene and dihydroocinene, single ring alicyclic dienes, such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and

1,5-cyclododecadiene and fused alicyclic and bridged ring multiple ring dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo (2,2,1) -hepta-2,5-diene;

alkenyl, alkylidene, cycloalkenyl and cycloalkylidenonorbornenes, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene. Of the dihydes typically used to prepare EPDMs, particularly preferred ones are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene ( MNB) and dicyclopentadiene (DCPD). Especially preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be prepared according to embodiments of the invention are elastomeric ethylene interpolymers, a C3 -C20 α-olefin / especially propylene, and optionally one or more diene monomers. Preferred Q-olefins for this embodiment of the present invention are designated by the formula CH2 = CHR *, where R * is a straight or branched alkyl group of 1 to 12 carbon atoms. Examples of suitable o-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. A particularly preferred α-olefin is propylene. Propylene-based polymers are generally referred to in the art as EP or EPDM polymers. Suitable dienes for use in the preparation of such polymers, especially multiblock EPDM-type polymers, include cyclic or polycyclic or straight chain diene conjugated or unconjugated dienesconjugates comprising from 40 to 20 carbons. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene, and 5-butylidene-2-norbornene. An especially preferred diene is 5-ethylidene-2-norbornene.

Because diene-containing polymers comprise alternating segments or blocks containing larger or smaller amounts of diene (including none) and ce-olefin (including none), the total amount of diene and olefin may be reduced without any doubt later polymer properties. That is, because diene and ce-olefin monomers are preferably incorporated into a single type of polymer block rather than uniformly or randomly throughout the polymer, they are more efficiently used and subsequently the cross-linking density of the polymer can be better. controlled. Such crosslinkable elastomers and cured products have advantageous properties, including increased tensile strength and improved elastic recovery.

In some embodiments, the interpolymers of the invention made with two catalysts incorporating different comonomer amounts have a weight ratio of blocks formed from 95: 5 to 5: 95. Elastomeric polymers desirably have an ethylene content of 20 to 90 percent, a diene content of 0.1 to 10 percent, and an α-olefin content of 10 to 80 percent, based on the total weight of the polymer. Even more preferably, the multiblock elastomeric polymers have an ethylene content of 60 to 90 percent, a diene content of 0.1 to 10 percent, and a 10% to 40 percent ce-olefin content based on the total polymer weight. . Preferred polymers are high molecular weight polymers having a weight average molecular weight (Mw) of from 10,000 to about 2,500,000, preferably from 20,000 to 500,000, more preferably from 20,000 to 350,000 and a polydispersity of less than 3.5, more preferably less than 3.0, and a Mooney viscosity (ML (1 + 4) 125 ° C) of 1 to 250. More preferably, such polymers have an ethylene content of 65 to 75 percent, a diene content of 0 to 6 percent, and a α-olefin of 20 to 35 percent.

Ethylene / α-olefin interpolymers may be functionalised by incorporating at least one functional group into their polymeric structure. Representative functional groups may include, for example, ethylenically unsaturated mono and di-functional carboxylic acids, mono and ethylenically unsaturated carboxylic acid anhydrides, salts thereof and esters thereof. Such functional groups may be grafted to an ethylene / α-olefin interpolymer, or may be copolymerized with ethylene and an optional comonomer to form an ethylene interpolymers, the functional comonomer and optionally other comonomer (s). Means for grafting polyethylene functional groups are described, for example, in U.S. Pat. 4,762,890, 4,927,888 and 4,950,541, the disclosures of which are incorporated herein by reference in their entirety. A particularly useful functional group is malic acid anhydride.

The amount of the functional group present in the interpolymers may vary. The functional group may typically be present in a copolymer-functionalized interpolymer in an amount of at least about 1.0, preferably at least about 5 percent by weight, and more preferably at least 7 percent by weight. The functional group will typically be present in a copolymer-functionalized interpolymer in an amount of less than about 40 weight percent, preferably less than about 30 weight percent, and more preferably less than about 25 weight percent.

Test Methods

In the following examples, the following analytical techniques are employed:

GPG Method for Samples 1-4 and A-C

An automated liquid handling robot equipped with a heated needle set at 160 ° C is used to add sufficient 1,2,4-trichlorobenzene stabilized with 300 ppm Ionol to each dried polymer sample to give a final concentration of 30mg / ml. A small glass stirring rod is placed in each tube and the samples heated to 160 ° C for 2 hours on a heated orbital shaker spinning at 250 rpm. The concentrated polymer solution is then diluted to 1 mg / ml using the automated liquid handling robot and the heated needle set at 160 ° C.

A Symyx Rapid GPC system is used to determine molecular weight data for each sample. A Gilson 350 pump set at a flow rate of 2.0ml / min is used to pump 1,2-dichlorobenzene purged with stabilized helium with 300 ppm Ionol as a fasemobile through three 10 micrometer (/ xm) Plgel columns B 300mm x 7.5 mm in series and heated to 160 ° C. A Polymer Labs ELS 1000 detector is used with Evaporator set at 250 ° C, Mist is set at 165 ° C and denitrogen flow rate set at 1.8 SLM at a pressure of 60-80 psi (400-600 kPa) N2 . The polymer samples are heated to 160 ° C and each sample injected into a 250 ° loop using the liquid handling robot and a heated needle. Serial analysis of the polymer samples is used using two linked loops and overlapping injections. Sample data is collected and analyzed using Symyx Epoch ™ Software. Manually integrated picosses and reported pesomolecular information uncorrected against a standard polystyrene calibration curve.

Standard CRYSTAF Method

Branch distributions are determined by crystallization analysis fractionation (CRYSTAF) using a CRYSTAF 200 unit from PolymerChar, Valencia, Spain. Samples are dissolved in 1,2,4-trichlorobenzene at 160 ° C (0.66mg / mL) for 1 hour and stabilized at 95 ° C for 45 minutes. Both temperatures range from 95 to 30 ° C at a cooling rate of 0.2 ° C / min. An infrared detector is used to measure the concentrations of the polymer solution. The cumulative soluble concentration is measured as the polymer crystallizes while the temperature is reduced. The analytical derivative of the cumulative profile reflects the short-chain branching distribution of the polymer.

The CRYSTAF peak temperature and area identified by the peak analysis module included in the CRYSTAF software (Version 2001.b, PolymerChar, Valencia, Spain). The CRYSTAF peak identification routine identifies a peak temperature as a maximum on the dW / dT curve and the area between the largest positive inflections on any side of the peak identified on the bypass curve. To calculate the CRYSTAF curve, the preferred processing parameters have a temperature limit of 70 ° C and smoothing parameters above the temperature limit of 0.1, and below the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 1-4 and A-C)

Exploratory Differential Calorimetry results are determined using a Q1000 DSC TAI model equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml / min is used. The sample is pressed into a thin film and melted in the press at about 175 ° C and then air-cooled to room temperature (25 ° C). 3-10 mg of material is then cut into a precision weighed 6mm diameter disc placed in a lightweight aluminum container (ca 50 mg) and then sealed. The thermal behavior of the sample is investigated with the following temperature profile. The sample is rapidly heated to 180 ° C and isothermal for 3 minutes to remove any previous thermal history. The sample is then cooled to -4 ° C at a cooling rate of 10 ° C / min and maintained at -40 ° C for 3 minutes. The sample is then heated to 150 ° C at a heating rate of 10 ° C / min. The cooling and second heating curves are recorded.

The DSC melt peak is measured as the maximum heat flow rate (W / g) with respect to the linear reference line drawn between -30 ° C and the end of the melt. Melt heat is measured as the area under the curve. melting at -30 ° C to the end of the melt using a linear reference line.

GPC Method (Excluding Samples 1-4 and A-C)

The gel permeation chromatographic system consists of a Polymer Laboratories Model PL-210 instrument or a Polymer Laboratories Model PL-220 instrument. The column and carousel compartments are operated at 140 ° C. Three 10 micron Mixed-B columns from Polymer Laboratories are used. The solvent is 1,2,4-trichlorobenzene. Samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm butylated hydroxytoluene (BHT). Samples are prepared by shaking for 2 hours at 160 ° C. The injection volume used is 100 microliters and the flow rate is 1.0ml / min.

The calibration of the GPC column assembly is performed with 21 narrow molecular weight polystyrene standards with molecular weights ranging from 580 to 8,400,000 arranged in 6 "cocktail" mixtures with at least a decade of separation between individual molecular weights. Standards are purchased from PolymerLaboratories (Shrospshire, UK). Polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights greater than 1,000,000 and 0.05 grams in 50 milliliters solvent for molecular weights less than 1,000,000. Polystyrene standards are dissolved at 80 ° C with light. stirring for 30 minutes. Mixtures of standard patterns are performed first and in the highest descending order of molecular weight to minimize degradation. Peak molecular weights of polystyrene standard are converted to molecular weights of polyethylene using the following equation (as described in Williams and Ward, J. Polym.Sei., Polym.Let. 6,621 (1968)): Mpoliethylene = 0.431 (Mpoestyrene).

Polyethylene equivalent molecular weight calculations performed using Viscotek TriSECversion 3.0 software.

Permanent Deformation to Compression

Permanent compression deformation is measured according to ASTM D 395. The sample is prepared by stacking 25.4 mm diameter round sediments at the thickness of 3.2 mm, 2.0 mm, and 0.25 mm until a total thickness of 10 mm is reached. 12.7 mm. Discs are cut from 12.7cm x 12.7cm compression molded plates with a hot press under the following conditions: zerodurant pressure 3 minutes at 190 ° C, followed by 86 MPa for 2 minutes at 190 ° C, followed by cooling within the press with cold running water at 86 MPa.

Density

Density samples are prepared according to ASTM D 1928. Measurements are made within one hour of sample pressing using ASTM D792 Method B.

Flexing Module / Secant / Storage Module

Samples are compression molded using ASTMD1928. Flexing and 2% secant modules are measured according to ASTM D-790. The storage module is measured according to ASTM D-5026-01 or equivalent technique. Optical Properties

0.4mm thick films are compression molded using a hot press (Carver Model # 4095-4PR1001R). The pellets are placed between polytetrafluoroethylene sheets, heated to 190 ° C at 55 psi (380kPa) for 3 minutes, followed by 1.3 MPa for 3 minutes, and then 2.6 MPa for 3 minutes. The film is then cooled in the press with cold running water at 1.3MPa for 1 minute. Compression molded films are used for optical measurements, tensile behavior, recovery and stress relaxation. Transparency is measured using a BYK Gardner Haze-gard as specified in ASTM D 1746.

The 45 ° brightness is measured using a BYK Garner 45 ° Microgloss Brightness Meter as specified inASTM D-2457.

Internal opacity is measured using a BYK GardnerHaze-gard based on ASTM D 1003 Procedure A. Oil is applied to the film surface to remove surface scratches.

Mechanical Properties - Tensile, Hysteresis and Rupture

The stress-strain behavior at uniaxial stress is measured using microtensile samples according to ASTM D1708. Samples are distended with an Instron at 500% min "1 at 21 ° C. Tensile strength and elongation at break are reported from an average of 5 samples. 100% and 300% hysteresis is determined from up to 100 cargacyclic % and 300% deformations using ASTM D 1708 microtensile samples with an Instron ™ instrument. The sample is loaded and unloaded at 267 min-1 for 3 cycles at 21 ° C. The 300% and 80 ° C cyclic experiments are conducted using an environmental chamber. In the experiment at 80 ° C, the sample is allowed to equilibrate for 45 minutes at the test tester temperature. In the cyclic experiment with 300% deformation and 21 ° C, the retraction stress at 150% deformation of the first discharge cycle is recorded. Percent recovery for all experiments is calculated from the first discharge cycle using the strain at which the load returned to the reference line. Percentage recovery is defined as:

<formula> formula see original document page 49 </formula>

where 8f is the deformation considered for the cyclic load ess is the deformation at which the load returns to the reference line during the first discharge cycle.

Stress relaxation is measured at a strain of 50 percent and 37 ° C for 12 hours using an INSTRON ™ instrument equipped with an environmental chamber. The calibration geometry was 7.6 mm x 25 mm x 0.4 mm. Equilibrium at 37 ° C for 45 minutes in the environmental chamber, the sample was distended to 50% strain at 333% min ~ 1. The voltage was recorded as a function of the 12 hour tempodurant. Percent stress relaxation after 12 hours was calculated using the formula:

<formula> formula see original document page 49 </formula>

where L0 is the load at 50% strain at 0 hours and Li 2 is the load at 50% strain after 12 hours.

Tensile notch rupture experiments are conducted on samples having a density of 0.88g / cc or less using an INSTRON ™ instrument. Ageometry consists of a 76mm x13mm x 0.4mm measurement section with a 2mm notch cut in the sample half of its length. The sample is stretched at 508mm min "1 to 21 ° C until it breaks. The breaking energy is calculated as the area under the stress-elongation curve until the maximum load is deformed. An average of 3 samples is reported.

TMAA Thermal Mechanical Analysis (Penetration Temperature) is conducted on compression molded discs 30mm in diameter x 3.3mm thick, formed at 180 ° C and 10 MPa molding pressure for 5 minutes and then rapidly air-cooled. The instrument used is Perkin Elmer's TMA 7. In the test, a 5mm radius tip probe (P / N N519-0416) is applied to the IN-force sample disc surface. The temperature is raised at 5 ° C / min from 25 ° C. The penetration distance of the probe is measured as a function of temperature. The experiment ends when the probe has penetrated 1mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression molded discs formed in a hot press at 180 ° C at a pressure of 10 MPa for 5 minutes and then water cooled in the press at 90 ° C / min. The test is conducted using a tension controlled rheometer (TAInstruments) equipped with double cantilever fixings for torsion testing.

A 1.5mm plate is pressed and cut into a 32xl2mm bar. The sample is fixed at both ends between 10 mm separate fixings (AL handle separation) and subjected to successive steps of -10 ° C to 200 ° C (5 ° C per step). At each temperature, the torsion modulus G 'is measured at an angular frequency of 10 rad / s, the strain range being maintained between 0.1 percent and 4 percent to ensure sufficient torque and that the measurement remains in the linear regime.

An initial static force of 10g is maintained (self-tensioning mode) to prevent sample loosening when thermal expansion occurs. As a result, the separation of AL handle increases with temperature, especially above the melting or softening point of the polymer sample. The test stops at the maximum temperature or when the spacing between the fixtures reaches 65 mm. Fusion Index

The melt index, or I2, is measured according to ASTM D1238, Condition 190 ° C / 2.16 kg. The melt index, or I101 is also measured according to ASTM D 1238, Condition 190 ° C / 10 kg.

ATREF

Analytical Temperature Elevation Elution Fractionation (ATREF) analysis is conducted according to the method described in USP 4,798,081 and Wilde, L .; Ryle, T.R. Knobeloch, D.C .; Peat, I.R .; From termination of BranchingDistributions in Polyethylene and Ethylene Copolymers, J. Polym Know. , 20, 441-455 (1982), which are hereby incorporated by reference in their entirety. The composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel ball) by slowly reducing the temperature to 20 ° C at a cooling rate of 0.1 ° C / min. The column is equipped with an infrared detector. A TREF chromatogram curve is then generated by eluting the crystallized sample from the column polymer and slowly increasing the temperature of the elution solvent (trichlorobenzene) from 20 to 120 ° C at a rate of 1.5 ° C / min.

13C NMR Analysis

Samples are prepared by adding approximately 3g of a 50/50 mixture of tetrachloroethane-d2 / orthodichlorobenzene to a 0.4g sample in an NMR10mm tube. The samples are dissolved and homogenized by heating the tube and its contents to 150 ° C. Data are collected using a JEOL ECLIPSE ™ 400 MHZ spectrometer or a Varian Unity PLUS ™ 400 MHz spectrometer, corresponding to a 13.5 resonance frequency of 100.5 MHz. Data are acquired using 4000 transients per data file with a pulse-repeating delay. 6 seconds To get the minimum noise signal for quantitative analysis, multiple data files are added. The spectral width is 2.0 5.0 Hz with a minimum deducted point file size of 32K. Samples are analyzed at 130 ° C in a 10mm wide band probe. Decomere incorporation is determined using a Randall triad method (Randall, J.C .; JMS-Rev.Macromol.Chem.Phys., C29,201-317 (1989) incorporated herein by reference in its entirety.

Polymer Fractionation by TREF

Large-scale TREF fractionation is conducted by dissolving 15-20g of polymer in 2 liters of 1,2,4-trichlorobenzene (TCB) while stirring for 4 hours at 160 ° C. The polymer solution is forced with 15 psig (100 kPa) denitrogen on a 3 inch by 4 ft (7.6 cm x 12 cm) steel column loaded with a 60:40 (v: v) mixture of 15 quality spherical glass globules. 30-40 (600-425 / xm) mesh technique (from Potters Industries, HC 30 Box 20, Brownwood, TX, 76801) and a 0.02 8 "diameter (0.7mm) stainless steel cut-out ball Pellets, Inc.63 Industrial Drive, North Tonawanda, NY 14120.) The column was immersed in a thermally controlled oil jacket, initially set at 160 ° C. The column is first ballistically cooled to 125 ° C, and then slowly cooled to 20 ° C. at 0.04 ° C per minute and kept for 1 hour Fresh TCB is introduced at about 65 ml / min while the temperature is increased by 0.167 ° C per minute.

Approximately 2,000 ml eluent portions of the preparative TREF column are collected on a 16 station heated fraction collector. The polymer is concentrated to each fraction using a rotary evaporator until about 50 to 100 ml of the polymer solution remains. Concentrated solutions are allowed to stand overnight before addition of excess methanol, filtration and rinsing (approx. 300-500 ml methanol including rinsing). The filtration step is performed in a vacuum assisted 3-position filtration station using 5.0 µm depolytetrafluoroethylene coated filter paper (from Osmonics Inc., Cat. # Z50WP04750). The filtered fractions are dried overnight in a vacuum oven at 60 ° C and weighed on an analytical balance before further testing.

Cast Resistance

Melt Resistance (MS) is measured using a capillary rheometer fitted to a 20: 1 matrix with a diameter of 2.1mm with an entry angle of approximately 45 degrees. After balancing the samples at 190 ° C for 10 minutes, the piston is operated at a rate of 1 inch / minute. The standard test temperature is 190 ° C. The sample is pulled uniaxially into a set of acceleration spaces located 100m below the matrix with an acceleration of 2.4mm / sec2. The required tensile force is recorded as a function of the compression speed of the compression cylinders. The maximum tensile strength obtained during the test is defined as the melt strength. In the case of polymer melt exhibiting tensile resonance, the tensile force before the onset of tensile resonance was considered as melt strength. Defined resistance is recorded in centiNewtons ("cN").

Catalysts

The term "overnight" refers to a time of approximately 16-18 hours, the term "ambient temperature" refers to a temperature of 20-25 ° C and the term "mixed alkanes" refers to a commercially mixed mixture. obtained from commercially available C6-9 aliphatic hydrocarbons under the trademark ISOPAR E® of ExxonMobil Chemical Company. If the name of a compound in the present invention is not in accordance with its structural representation, the structural representation will have priority. The synthesis of all metal complexes and the preparation of all screening experiments were conducted in a dry nitrogen atmosphere using dry box techniques. All solvents used were HPLC grade and dried before use. MMAO refers to modified methylalumoxane, a triisobutylaluminum modified methylalumoxane marketed by Akzo Nobel Corporation.

Catalyst (BI) preparation is conducted as follows.

a) Preparation of (1-methylethyl) (2-hydroxy-3,5-di (t-butyl) phenyl) methylimine

3,5-Di-t-Butylsalicylaldehyde (3.0g) is added to 10ml of isopropylamine. The solution turns light yellow. After stirring at room temperature for 3 hours, volatiles are removed under vacuum to give a pale yellow crystalline solid (97 percent yield).

b) Preparation of dibenzyl 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (1-methylethyl) imino) methyl) (2-oxoyl) zirconium

A solution of (1-methylethyl) (2-hydroxy-3,5-di (t-butyl) phenyl) imine (605mg, 2.2 mmol) in 5 mL of toluene is slowly added to a solution of Zr (CH 2 Ph) 4. (500mg, 1.1 mmol) in 50 ml of toluene. The resulting dark yellow solution is stirred for 30 minutes. The solvent is removed under reduced pressure to give the desired product as a reddish brown solid.

Preparation of catalyst (B2) is conducted as follows. (A) Preparation of (1- (20-methylcyclohexyl) ethyl) (2-oxy-3,5-di (t-butyl) phenyl) imine

2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol (90 mL) and di-t-butylsalicaldehyde (10.0g, 42.67 mmol) is added. The reaction mixture is stirred for three hours and then cooled to -25 ° C for 12 hours. The resulting yellow solid precipitate is collected by filtration and washed with cold methanol (2 x 15ml) and then dried under reduced pressure. The yield is 11.17 g of a yellow solid. 1HNMR is compatible with the desired product as a mixture of isomers.b) Preparation of dibenzyl bis (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imino) zirconium

A solution of bis (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imine (7.63g, 23.2 mmol) in 200 ml of toluene is slowly added. Added to a solution of Zr (CH 2 Ph) 4 (5.28 g, 11.6 mmol) in 600 mL of toluene. The resulting dark yellow solution is stirred for 1 hour at 25 ° C. The solution is diluted with 680 ml of toluene to give a solution with a concentration of 0.00783M.

Cocatalyst 1. A mixture of methyldi (C1-4 alkyl) ammonium detetracis (pentafluorophenyl) borate salts (hereinafter referred to as Armenian borate) prepared by reaction with a long trialkylamine (ARMEEN ™ M2HT, from Akzo Nobel, Inc.), HCl eLi [B (C6F5) 4], substantially as described in USP5,919,9883, Ex. 2.

Cocatalyst 2 - Mixed C 1-18 alkyl dimethyl ammonium bis (tris (pentafluorophenyl) -2-undecylimidazolide salt prepared according to USP 6,395,671, Ex. 16.

Transfer Agents. The transfer agents employed include diethylzinc (TEN, SAI), di (i-butyl) zinc (SA2), di (n-hexyl) zinc (SA3), triethylaluminum (TEA, SA4), trioctylaluminum (SA5), triethylgium (SA6) , i-butylaluminum bis (dimethyl (t-butyl) siloxane) (SA7), i-butylaluminum bis (di (trimethylsilyl) amide) (SA8), n-octylaluminum di (pyridine-2-methoxide) (SA9), bis (n-octadecyl) i-butylaluminum (SAIO), i-butylaluminumbis (di (n-pentyl) amide) (SA11), n-octylaluminum bis (2,6-di-t-butylphenoxide) (SA12), n- octylaluminium di (ethyl (1-naphthyl) amide) (SA13), ethylaluminum bis (t-butyldimethylsiloxide) (SA14), ethylaluminum di (bis (trimethylsilyl) amide) (SA15), ethylalumininiumbis (2,3,6,7-dibenzoyl) 1-azacycloheptanoamide) (SA16), n-octyl aluminum bis (2,3,6,7-dibenzo-1-azacyclohetanoamide) (SA17), n-octyl aluminum bis (dimethyl (t-butyl) siloxide (SA18), (2, 6-diphenylphenoxide) ethylzinc (SA19) and ethylzinc (t-butoxide) (SA20).

Examples 1-4, Comparative A-C

High Parallel Polymerization General Conditions

Productivity

The polymerizations are conducted using a high throughput parallel polymerization reactor (PPR) from Symyx Technologies, Inc. and operated substantially in accordance with USP's 6,248,540, 6,030,917, 6,362,309,6,306,658 and 6,316,663. Ethylene copolymerizations are conducted at 130 ° C and 200 psi (1.4 MPa) with ethylene on demand using 1.2 equivalents of cocatalyst 1 based on the total catalyst used (1.1 equivalents when MMAO- is present). A series of polymerizations are conducted in a parallel pressure reactor (PPR) containing 48 individual reactor cells in a 6x8 series which are equipped with a pre-weighed glass tube. The workload in each reactor cell is 6000file. Each cell has pressure and temperature controlled comagitation provided by individual stirring vanes. Monomer gas and rapid cooling gas are injected directly into the PPR unit and controlled by automatic valves. Liquid reagents are added robotically to each reactor cell through syringes and the reservoir solvent is alkanomix. The order of addition is solvent of mixed alkanes (4ml), ethylene, 1-octene comonomer (1ml), cocatalyst 1 or cocatalyst 1 / MMAO mixture, transfer agent and catalyst or decatalyst mixture. When a mixture of cocatalyst 1 and MMAO or a mixture of two catalysts is used, the reagents are premixed in a small vial immediately prior to addition to the reactor. When a reagent is omitted in an experiment, the order of addition above is maintained. Polymerizations are conducted for approximately 1-2 minutes until predetermined ethylene consumptions are reached. After rapid CO cooling, the reactors are cooled and the glass tubes discharged. The tubes are transferred to a centrifuge / vacuum drying unit and dried for 12 hours at 60 ° C. The dry polymer tubes are heavy and the difference between this weight and the empty weight gives the net yield of the polymer. Results are contained in Table 2. In Table 2 and elsewhere in the application, comparative compounds are indicated with an asterisk (*).

Examples 1-4 demonstrate the synthesis of block copolymers by the present invention as evidenced by the formation of a very narrow, essentially monomodal MWD copolymer when TEN is present and a broad, bimodal pesomolecular distribution product (a mixture of separately produced polymers) in the invention. absence of TEN. Because the fact that Catalyst (Al) is known to incorporate higher than Catalyst (BI), the different segment blocks of the resulting copolymers of the invention are distinguishable based on branching or density.

<table> table see original document page 58 </column> </row> <table>

1 C6 chain content or higher per 1000 carbons

Bimodal molecular weight distribution It can be seen that polymers produced according to the invention have relatively narrow polydispersity (Mw / Mn) and higher bloc copolymer content (trimer, tetramer, or higher) than polymers prepared in the absence of a transfer.

More characterizing data for the polymers of Table 1 are determined by reference to the Figures. More specifically, the DSC and ATREF results show the following:

The DSC curve for the polymer of Example 1 shows a melting point of 115.7 ° C (Tm) with a melting heat of 158.1 J / g. The corresponding CRYSTAF curve shows the highest peak at 34.5 ° C with a peak area of 52.9 percent. The difference between DSC Tm and TCrystaf is 81.2 ° C.

The DSC curve for the polymer of Example 2 shows a picom with a melting point of 109.7 ° C (Tm) with a melting heat of 214.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 46.2 ° C with a peak area of 57.0 percent. The difference between DSC Tm and TCrystaf is 63.5 ° C.

The DSC curve for the polymer of Example 3 shows a picom with a melting point of 120.7 ° C (Tm) with a heat fusion of 160.1 J / g. The corresponding CRYSTAF curve shows the highest peak at 66.1 ° C with a peak area of 71.8 percent. The difference between DSC Tm and TCrystaf is 54.6 ° C.

The DSC curve for the polymer of Example 4 shows a picom with a melting point of 104.5 ° C (Tm) with a heat fusion of 170.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 30 ° C with a peak area of 18.2 percent. The difference between DSC Tm and TCrystaf is 74.5 ° C. The DSC curve for Comparative Example A * shows a melting point of 90.0 ° C (Tm) with a fusion heat of 86.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 48 8.5 ° C with a peak area of 29.4 percent. The difference between DSC Tm and TCrystaf is 41.8 ° C. The DSC curve for Comparative Example B * shows a melting point of 12.9 ° C (Tm) with a melting heat of 237.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 82.4 ° C with a peak area of 83.7 percent. Both values are compatible with a resin whose density is high. The difference between DSC Tm and TCrystafé is 47.4 ° C.

The DSC curve for Comparative Example C * shows a melting point of 125.3 ° C (Tm) with a melting heat of 143.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 81.8 ° C with a peak area of 34.7 percent as well as a lower crystalline peak at 52.4 ° C. The separation between the two peaks is compatible with the presence of a high crystallinity and low crystallinity polymer. The difference between DSC Tm and TCrystaf is 43.5 ° C.

Examples 5-19 - Comparative Examples D * -F *, Continuous Solution Polymerization, Catalyst A1 / B2 + TENSContinuous solution polymerizations are conducted in a computer controlled autoclave reactor equipped with an internal stirrer. Exxon Mobil Chemical Company (ISOPAR ™) Alkaline Solvent Solvent, 2.70 lbs / hr (1.22 kg / hr) ethylene, 1-octene, and hydrogen (if used) are supplied to a 3.8 L reactor equipped with a temperature control jacket and an internal thermocouple. The reactor solvent feed is measured through a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and the pressure to the reactor. At the pump loading, a side stream is taken to provide jet streams to the catalyst and cocatalyst injection lines 1 and to the stirrer agitator. These flows are measured using Micro-Motion mass flow meters and controlled by control valves or by manual adjustment of needle valves. The remaining solvent is combined with 1-octene, ethylene, and hydrogen (when used) and fed to the reactor. A mass flow controller is used to release hydrogen to the reactor as needed. The temperature of the solvent / monomer solution is controlled by the use of a heat exchanger prior to entering the reactor. The current enters the bottom doreator. Catalyst component solutions are measured using pumps and overflow meters and are combined with the decatalyst wash solvent and introduced from the bottom of the reactor. The reactor is operated full of liquid at 500 psig (3.45 MPa) with vigorous comagitation. The product is removed by the exhaust lines at the top of the reactor. All doreator output lines are steam traced and insulated. The polymerization is stopped by the addition of a small amount of water to the outlet line together with any stabilizers or other additives and the mixture passed through a static mixer. Product chain is then heated by passing through a heat exchanger prior to devolatization. The polymer product is recovered by extrusion using a devolatizing extruder and water cooled pelletizer. Details and process results are contained in Table 2. Selected polymer properties are shown in Table 3. Table 2

Process Details for Preparation of Representative Polymers

<table> table see original document page 62 </column> </row> <table>

* Comparative Example, not an example of the invention

1 standard cm3 / min

2- [N- (2,6-di (1-methylethyl) phenyl) starch) (2-isopropylphenyl) (α-naphthalen-2-diyl) (6-pyridin-2-diyl) methane)] ammonium dimethyl

3 bis (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imino) zirconium dibenzyl

4 molar ratio in reactor

5 polymer production rate

6 weight percent ethylene conversion in reactor

7 efficiency, kg polymer / g M where g M = g Hf + g ZrTable 3

Properties of Representative Polymers

<table> table see original document page 63 </column> </row> <table>

Comparative Example, Not Example of Invention The resulting polymers are tested by DSC and ATREF as in the previous examples. The results are as follows:

The DSC curve for the polymer of Example 5 shows a picom with a melting point of 119.6 ° C (Tm) with a melting heat of 60.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 47.6 ° C with a peak area of 59.5 percent. The delta between DSC Tm and TCrystaf is 72.0 ° C. The DSC curve for the polymer of Example 6 shows a picocum of melting point of 115.2 ° C (Tm) with a heat of 60.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 44.2 ° C with a peak area of 62.7 percent. The delta between DSC Tm and TCrystaf is 71.0 ° C. The DSC curve for the polymer of Example 7 shows a picocommel of 121.3 ° C (Tm) with a melting heat of 69.1 J / g. The corresponding CRYSTAF curve shows the highest peak at 49.2 ° C with a peak area of 29.4 percent. The delta between DSC Tm and TCrystaf is 72.1 ° C. The DSC curve for the polymer of Example 8 shows a melting point of 123.5 ° C (Tm) with a melting heat of 67.9 J / g. The corresponding CRYSTAF curve shows the highest peak at 80.1 ° C with a peak area of 12.7 percent. The delta between DSC Tm and TCrystaf is 43.4 ° C. The DSC curve for the polymer of Example 9 shows a melting point of 124.6 ° C (Tm) with a melting heat of 73.5 J / g. The corresponding CRYSTAF curve shows the highest peak at 80.8 ° C with a peak area of 16.0 percent. The delta between DSC Tm and TCrystaf is 43.8 ° C. The DSC curve for the polymer of Example 10 shows a melting point of 115.6 ° C (Tm) with a melting heat of 60.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 40.9 ° C with a peak area of 52.4 percent. The delta between DSC Tm and TCrystaf is 74.7 ° C. The DSC curve for the polymer of Example 11 shows a melting point of 113.6 ° C (Tm) with a melting heat of 70.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 39.6 ° C with a peak area of 25.2 percent. The delta between DSC Tm and TCrystaf is 74.1 ° C. The DSC curve for the polymer of Example 12 shows a melting point of 113.2 ° C (Tm) with a melting heat of 48.9 J / g. The corresponding CRYSTAF curve shows no peak equal to or greater than 30 ° C (Tcrystaf for further calculation is therefore set at 30 ° C). The delta between DSC Tm and TCrystaf is 83.2 ° C. The DSC curve for the polymer of Example 13 shows a melting point of 114.4 ° C (Tm) with a melting heat of 49.4 J / g. . The corresponding CRYSTAF curve shows the highest peak at 33.8 ° C with a peak area of 7.7 percent. The delta between DSC Tm and TCrystaf is 84.4 ° C. The DSC curve for the polymer of Example 14 shows a melting point of 12.8 ° C (Tm) with a melting heat of 127.9 J / g. . The corresponding CRYSTAF curve shows the highest peak at 72.9 ° C with a peak area of 92.2 percent. The delta between DSC Tm and TCrystaf is 47.9 ° C. The DSC curve for the polymer of Example 15 shows a melting point of 114.3 ° C (Tm) with a melting heat of 36.2 J / g. The corresponding CRYSTAF curve shows the highest peak at 32.3 ° C with a peak area of 9.8 percent. The delta between DSC Tm and TCrystaf is 82.0 ° C. The DSC curve for the polymer of Example 16 shows a melting point of 116.6 ° C (Tm) with a melting heat of 44.9 J / g. The corresponding CRYSTAF curve shows the highest peak at 48.0 ° C with a peak area of 65.0 percent. The delta between DSC Tm and TCrystaf is 68.6 ° C. The DSC curve for the polymer of Example 17 shows a melting point of 116.0 ° C (Tm) with a melting heat of 47.0 J / g. . The corresponding CRYSTAF curve shows the highest peak at 43.1 ° C with a peak area of 56.8 percent. The delta between DSC Tm and TCrystaf is 72.9 ° C. The DSC curve for the polymer of Example 18 shows a picocum with a melting point of 120.5 ° C (Tm) with a heat fusion of 141.8 J / g. The corresponding CRYSTAF curve shows the highest peak at 70.0 ° C with a peak area of 94.0 percent. The delta between DSC Tm and TCrystaf is 50.5 ° C. The DSC curve for the polymer of Example 19 shows a picocompatible melting point of 124.8 ° C (Tm) with a melting heat of 174.8 J / g. The corresponding CRYSTAF curve shows the highest peak at 79.9 ° C with a peak area of 87.9 percent. The delta between DSC Tm and TCrystaf is 45.0 ° C. The DSC curve for the polymer of Comparative Example D * shows a peak with a melting point of 37.3 ° C (Tm). / g. The corresponding CRYSTAF curve shows the highest peak at 30.0 ° C. These two values are compatible with a resin whose density is low. The delta between DSC Tm and TCrystaf is 7.3 ° C.

The DSC curve for the polymer of Comparative Example E * shows a peak with a melting point of 124.0 ° C (Tm) of a melting heat of 179.3 J / g. The corresponding CRYSTAF curve shows the highest peak at 79.3 ° C with a peak area of 94.6 percent. These two values are compatible with a resin whose density is high. The deltaentre DSC Tm and TCrystaf is 44.6 ° C.

The DSC curve for the polymer of Comparative Example F * shows a peak with a melting point of 124.8 ° C (Tm) of common melting heat of 90.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 77.6 ° C with a peak area of 19.5 percent. The separation between the two peaks is compatible with the presence of both high crystallinity polymer and low crystallinity polymer. The delta between DSC Tm and TCrystaf is 47.2 ° C.

Physical Property Test

Polymer samples are evaluated for physical properties such as high temperature resistance properties, as proven by TMA temperature test, slug block resistance, high temperature recovery, compression deformation and storage modulus ratio, G "(25 ° C) / G '(100 ° C) Several commercially available polymers are included in the tests: Comparative G * is a substantially linear ethylene / 1-octene copolymer (AFFINITY®, from The Dow ChemicalCompany), Comparative H * is an ethylene / Substantially linear 1-elastomeric octene (AFFINITY®EG8100 of The Dow Chemical Company), Comparative Example 1 * is a substantially linear ethylene / 1-octene copolymer (AFFINITY® PL1840 of The Dow Chemical Company), Comparative Example J * is a styrene / butadiene / styrene triblock copolymer (KRATON ™ G1652 from KRATONPolymers), Comparative Example K * is a vulcanized moplastic (TPV, a polyolefin blend containing a dispersed crosslinked elastomer). Results are presented in Table 4.

Table 4

High Temperature Mechanical Properties

<table> table see original document page 67 </column> </row> <table> <table> table see original document page 68 </column> </row> <table>

In Table 4, Comparative Example F * (which is a physical mixture of the two polymers resulting from simultaneous polymerizations using catalyst Al and B1) has a penetration temperature of 1 mm of about 70 ° C, whereas Examples 5-9 have a temperature of penetration lmm of 100 ° C or higher. In addition, examples 10-19 have a delmm penetration temperature greater than 85 ° C, with most having a TMA temperature of 1mm greater than 90 ° C or even higher than 100 ° C. This shows that new polymers have better dimensional stability at higher temperatures compared to a physical mixture. Comparative Example J * (a commercial SEBS) has a 1mm boat temperature of about 107 ° C, but a very precarious compression permanent deformation of about 100%, and also failed to recover during a 300 ° deformation recovery. % at high temperature (80 ° C). Thus, the exemplified polymers have an unprecedented combination of properties not available even in some high performance elastomers found in the trade.

Similarly, Table 4 shows a low (good) G '(25 ° C) / G "(100 ° C) storage modulus ratio for the polymers of the invention of 6 or less, with a physical mixture (Comparative Example F *) has a storage modulus ratio of 9 and a random ethylene / octene copolymer (Comparative Example G *) of similar density has a storage modulus ratio of greater magnitude (89). such polymers will not be relatively affected by temperature, and articles made of such polymers may be usefully employed over a wide temperature range.This feature of low storage modulus and temperature independence is particularly useful in elastomer applications such as formulations. pressure sensitive adhesives.

The data in Table 4 also show that the inventive polymers have improved pellet blocking strength. In particular, Example 5 has a pellet blocking resistance of 0 MPa, meaning that it is free-flowing under the tested conditions compared to Comparative Examples F * and G * which show considerable blocking. Blocking strength is important since bulk shipment of polymers with high blocking strengths can result in glutination and product adhesion when storing or shipping.

The permanent high temperature (70 ° C) compression strain for the polymers of the invention is generally good, generally meaning less than about 80 percent, preferably less than about 70 percent, and especially less than about 60 percent. cent. In contrast, Comparative Examples F *, G *, H * and J * have a permanent compression strain at 70 ° C of 100 percent (the maximum possible value indicating no recovery). Good permanent high temperature compression deformation (low numerical values) is especially required for applications such as gaskets, window profiles, o-rings, and the like.

Mechanical Properties at Room Temperature

<table> table see original document page 70 </column> </row> <table> Table 5 shows results of the mechanical properties for the new polymers as well as for comparative room temperature polymers. It can be seen that the polymers of the invention have very good abrasion resistance when tested according to ISO4649, generally showing a volume of less than about 90 mm, preferably less than about 80 mm, and especially less than about 50 mm3. In this test, higher numbers indicate larger volume loss and consequently lower abrasion resistance.

The tensile strength, as measured by the tensile tear strength of the inventive polymers, is generally 100 mJ or greater, as shown in Table 6. The tensile strength of the inventive polymers may be as high as 3000 mJ, or as high. how much 5,000 mJ. Comparative polymers generally have tensile strengths of no more than 750 mJ. Table 5 also shows that the polymers of the invention have better shrinkage at 150 percent deformation (demonstrated by higher shrinkage values) than some comparative samples. Comparative Examples F *, G * and H * have a tensile value at 150 percent strain of 400 kPa or less. whereas the polymers of the invention have shrinkage stress values at a deformation of 150 percent from 500 kPa (Ex.11) to as high as about 1100kPa (Ex.17). Polymers with shrinkage stress values greater than 150 percent would be useful in elastic applications such as elastic fibers and especially nonwoven fabrics. Other applications include diapers, toiletries, medical waistband applications such as straps and waistband.

Table 5 also shows that stress relaxation (at 50% strain) is also improved (less) in the polymers of the invention compared, for example, to Comparative Example G *. Less stress relaxation means that the polymer better retains its strength in applications such as diapers and other garments where retention of elastic properties is desired over long periods of time at body temperatures.

Optical Test

Table 6

<table> table see original document page 72 </column> </row> <table>

The optical properties reported in Table 6 are based on substantially semi-orientated compression molded films. The optical properties of polymers may vary in wide ranges due to the variation in the size of the crystallite resulting from the variation in the amount of chain transfer agent employed in the polymerization.

Multiblock Copolymer Extraction

The polymer extraction studies of Examples 5, 7 and Comparative Example E * are conducted. In the experiments, the polymer sample is weighed into a glass frit extraction thimble and adapted to a Kumagawa type puller. The sample extractor is purged with nitrogen, and a 500 ml round bottom flask is charged with 350 ml diethyl ether. The vial is then adapted to the extractor. The ether is heated during stirring. Time is noted when the ether begins to condense on the thimble, and extraction is allowed to proceed under nitrogen for 24 hours. At this time, the heating is stopped and the solution allowed to cool. Any ether remaining in the extractor is returned to the vial. The ether in the flask is evaporated under vacuum at room temperature, and the resulting solids are dry purged with nitrogen. Any residue is transferred to a heavy flask using successive hexane washes. The combined hexanes washes are then evaporated with another nitrogen purge, and the residue dried under vacuum overnight at 40 ° C. Any ether remaining in the extractor is purged with nitrogen. A second round-bottomed clean flask with 350 ml hexane is then connected to the extractor. Hexane is heated to reflux with stirring and kept under reflux for 24 hours after the first time condensation of hexane on the thimble is observed. The heating is then stopped and the vial allowed to cool. Any remaining hexane in the extractor is transferred back to the flask. Hexane is removed by evaporation under vacuum at room temperature, and any residue remaining in the flask is transferred to a flask under successive hexane washes. The hexane in the flask is evaporated through nitrogen purge and the vacuum dried residue overnight at 40 ° C. Polymer sample remaining on the thimble after extraction is transferred from the thimble into a heavy flask and dried overnight at 40 ° Ç. The results are shown in Table 7. Table 7

<table> table see original document page 74 </column> </row> <table> Additional Examples 19 A-J Polymer, Continuous Solution Polymerization, Catalyst A1 / B2 + DEC

For Examples 19A-I

Continuous solution polymerizations are conducted in a well mixed computerized reactor. Purified mixed alkane solvent (ISOPAR ™ E from ExxonMobilChemical Company), ethylene, 1-octene, and hydrogen (if used) are combined and fed to a 27 gallon reactor. Reactor feeds are measured by mass-flow controllers. Supply chain temperature is controlled by use of a glycol-cooled heat exchanger prior to normal intake. Catalyst component solutions are measured using pumps and mass flow meters. The pump is operated full of liquid at a pressure of approximately 550 psig. Upon exiting the reactor, water and additives are injected into the polymer solution. The water hydrolyzes the catalysts, and completes the polymerization reactions. The post-reactor solution is then heated for preparation for a two-stage devolatization. The solvent and unreacted monomers are removed during the devolatization process. The polymer melt is pumped into a submerged pellet die.

For Example 19J

Continuous solution polymerizations are conducted in a computerized autoclave reactor equipped with an internal stirrer. Purified Mixed Alkane Solvent (IS0PAR ™ E from ExxonMobil Chemical Company), 2.70 lbs / hr (1.22 kg / hr) ethylene, 1-octene and hydrogen (if used) are supplied to a 3.8 L reactor equipped with shirt for temperature control and a thermoparinterno. Solvent feed to the reactor is measured via a mass flow controller. A variable-speed bombadiaphragm controls solvent flow rate and reactor pressure. At pump discharge, a side stream is taken to provide flushing flows to the ecocatalyst catalyst injection lines and reactor agitator. These flows are measured using Micro-Motion mass flow meters and controlled via control valves or through manual adjustment of needle valves. The remaining solvent is combined with 1-octene, ethylene, and hydrogen (when used) and fed to the reactor. A mass flow controller is used to release hydrogen into the reactor when needed. The temperature of the solvent / monomer solution is controlled by using a heat exchanger before entering the reactor. Current enters the bottom of the reactor. Catalyst decomposing solutions are measured using pumps and mass flow meters and are combined as a catalyst wash solvent and fed into the reactor bottom. The reactor is operated full of liquid at 500 psig (3.45 MPa) with vigorous stirring. The product is removed by the output lines at the top of the reactor. All reactor output lines are tracked with isolated vapor. Polymerization is stopped by adding a small amount of water to the outlet line together with any stabilizers or other additives and passing the mixture through a static mixer. The product stream is then heated by passing through a heat exchanger prior to devolatization. The polymeric product is recovered by extrusion using a water cooled devolatizing epellisizer extruder.

The details and results of the process are contained in Table 8. Selected polymer properties are shown in Tables 9A-C.

In Table 9B, examples of the invention 19F and 19G show low immediate deformation around 65-70% deformation after 50% elongation. Table 8 - Polymerization Conditions

<table> table see original document page 77 </column> </row> <table>

1 standard cm3 / min

2 [N- (2,6-di (1-methylethyl) phenyl) starch) (2-isopropylphenyl) (α-naphthalen-2-diyl) (6-pyridin-2-diyl) methane)] hafnium dimethyl

3 bis (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imino) zirconium dibenzyl

4 ppm in final product calculated by mass balance

5 polymer production rate

6 weight percent ethylene conversion in reactor

7 efficiency, kg polymer / g M where g M = g Hf + g ZrTable 9A - Physical Properties of Polymer

<table> table see original document page 78 </column> </row> <table>

Table 9B - Physical Properties of Compression Molded Film Polymer

<table> table see original document page 78 </column> </row> <table> Table 9C Average Block Index for Representative Polymers'

<table> table see original document page 79 </column> </row> <table>

Additional information regarding the calculation of block indices for the various polymers is described in U.S. Patent Application Serial No. (insert as known) entitled "Ethylene / a-Olef in Interpolymers" filed March 15, 2006, in the name of ColinL.P Shan, Lonnie Hazlitt, et al. , and granted to DowGlobal Technologies Inc., the disclosure of which is incorporated herein by reference in its entirety.

2 Zn / C2 * 1000 - (feed rate Zn * concentration Zn / 1000000 / Mw of Zn) (feed rate ethylenototal * (1-fractional ethylene conversion rate) / Mw deEt i 1 eno) * 10 0 0. Please note that "Zn11 to" Zn / C2 * 10 0 011 refers to the amount of zinc in diethyl zinc ("TEN") used in the polymerization process, and "C2" refers to the amount of ethylene used in the polymerization process.

COMPOSITIONS OF THIS INVENTION

The compositions of the present invention comprise the above-described ethylene / olefin interpolymer. While any density of the ethylene / cyolefin interpolymer may be useful, the lower the density, the more elastic the polymer. It is especially preferred that the density of the interpolymer is from about 0.85 to about 0.89 g / cc and even more preferably from about 0.86 to about 0.885 g / cc.

Casting Indexes of the Present Invention

The preferred melt index (12) of the interpolymer is generally about at least 0.5, preferably about at least 0.75 g / 10 min. Correspondingly, the preferred melt index (12) of the interpolymer is generally less than about 20g / 10min, sometimes less than about 1.5g / 10min. However, the preferred melt index may often depend on the desired conversion process, such as blown film, melt film, extrusion lamination, etc.

Blown Film

For blown film processes, the melt index (12) of the interpolymer is generally about at least 0.5, preferably at least about 0.75 g / 10min. The melt index (12) of the interpolymer is generally about 5 maximum, preferably about 3 g / 10 min maximum. In addition, it is often preferable that the ethylene / o-olefin interpolymer be made with a diethylzinc chain transfer agent where the zinc to ethylene ratio is about 0.03 x 10-3 to about 1.5 x 10-6. 3

Cast Film and Extrusion Lamination

For melt film and extrusion lamination processes, the melt index (12) of the interpolymer is generally about at least 0.5, preferably about at least 0.75, more preferably at least about 3, even more preferably. about 4g / 10 min. The melt index (12) of the interpolymer is generally about 20 maximum, preferably about 17 maximum, more preferably about 12 maximum, even more preferably about 5 g / 10 min maximum. In addition, it is often preferable that the ethylene / α-olefin interpolymer be made with a zinc chain transfer agent where the zinc to ethylene ratio is from about 0.03 x 10 -3 to about 1.5 x 10 -3. The composition may contain additional components, such as other empolyolefin-based plastomers and / or elastomers. Polyolefin-based elastomers and plastomers / polymers include the ethylene copolymers with at least one other (C3-C22) alpha-olefin / as well as propylene-copolymers with at least one other (C2, C4-C22) alpha-olefin. A second component is employed comprising low density high pressure resin. Possible materials for use as an additional component include LDPE (homopolymer); ethylene polymerized with one or more α-olefins, such as propylene or butene; and copolymerized ethylene with at least one α- / 3-ethylenically unsaturated comonomer, such as acrylic acid, methacrylic acid, methyl acrylate, and vinyl acetate, branched polypropylene and mixtures thereof. A suitable technique for preparing high pressure ethylene copolymer compositions is described by McKinney et al. In U.S. Patent 4,599,392, the disclosure of which is incorporated herein by reference.

LDPE (homopolymer) is often the most preferred material for use as an additional polymeric component. Low-density, high-pressure polyethylene (LDPE) material has a melt index MI (12) of less than about 20, more preferably less than about 5, most preferably less than 1, and greater than about 0.2, more preferably greater than about 0.25, most preferably greater than 0.3g / 10 min. The preferred LDPE will have a density between about 0.915 g / cm3 and 0.93 g / cm3, with less than 0.92 g / cm3 being more preferred.

LDPE will ideally be added in an amount such that it comprises at least about 1 percent, more preferably at least about 4 percent, and most preferably about 6 percent by weight of the final composition. Preferably, the LDPE will not comprise more than 12 percent, preferably no more than 10, even more preferably no more than 8 percent, and most preferably between 4 and 7 percent by weight of the final composition. It will be appreciated that the total amount of the ethylene / α-olefin eLDPE interpolymer need not necessarily be 100% as other materials that may be present.

In another embodiment of the present invention, a third polymer component may be used to improve compatibility, miscibility, dispersion, or other characteristics between the polymeric components as is generally known in the prior art.

LDPE may be made in an autoclave or stubular reactors capable of operating at pressures above 14,500psi (100 MPa) using free radical initiators such as peroxides, but it is preferred that these components be made in an autoclave reactor (optionally configured with one tubular reactor in series) cooled ethylene feed below 35 ° C operating in single phase mode with three or more zones. The reactor is preferably operated above the transition point (phase boundary between a two-phase and single phase system) at an average reactor temperature of approximately 240 ° C. The composition of the present invention may also include LDPE / LDPE mixtures, where one of the LDPE resins has a relatively higher melt index and the other has a lower melt index and is more branched. The component with the highest melt index can be obtained from a tubular reactor and a lower MI component and higher branch mix can be added in a separate extrusion step or using a parallel / autoclave tubular reactor in combination with special methods to control the melt index. of each reactor, such as telomere recovery in the recycling stream or by adding fresh ethylene to the autoclave reactor (AC) or any other known methods in the art state.

For additional attributes, any of the polymer components can be functionalized or modified at any stage. Examples include, but are not limited to graft, crosslinking, or other cross-functionalization methods.

Film layers comprising the composition of the present invention are often capable of stress relaxation of at most about 60, preferably about at most 40, more preferably at least about 28% to 75% strain at 100 ° F for at least 10 hours. .

Mixture Preparation

If a mixture is to be employed it may be prepared by any means known in the art, including rotary drum dry mixing, weighing feed, solvent mixing, compound extrusion melt or side arm or similar combinations, and combinations thereof. .

The compositions of the present invention may also be mixed with other materials, such as polypropylene and ethylene styrene interpolymers, as well as SEBS, SIS, SBS and other styrenic block copolymers. These other materials may be mixed with the composition of the invention to modify, for example, processing characteristics, film resistance, thermal sealing or adhesion.

The components of the mixtures of the present invention may be used in a chemically and / or physically modified form to prepare the composition of the invention. Such modifications may be made by any known technique, such as, for example, by deionomerization and extrusion grafting.

Additives such as antioxidants (eg impedidostal phenolics such as Irganox® 1010 or Irganox®1076 provided by Ciba Geigy), phosphites (eg Irgafos®168 also supplied by Ciba Geigy), adhesion additives (eg PIB), Standostab PEPQ ™ (supplied by Ciba Geigy). Sandoz), pigments, dyes, fillers, and the like may also be included in the ethylene polymer extrusion composition of the present invention as long as they do not interfere with the reduced stretch resonance discovered by the depositors. The article made of or utilizing the inventive composition may also contain additives to increase anti-blocking and anti-friction characteristics including, but not limited to, treated and untreated silicon adoxide, talc, calcium carbonate, and clay as well as primary, secondary and substituted acid oxide, cooling cylinder deliberation agents, desilicone coatings, etc. Other additives may also be added to enhance the anti-fog characteristics of, for example, transparent fused films, as described, for example, by Niemann in U.S. Patent No. 4,486,552, the disclosure of which has been incorporated herein by reference. Still other additives, such as quaternary ammonium compounds alone or in combination with ethylene-acrylic acid (EAA) copolymers or other functional polymers, may also be added to enhance the antistatic characteristics of coatings, profiles and films of the present invention and to allow, for example, packaging and manufacture of electronically sensitive products. Other functional polymers such as maleic grafted polyethylene with maleic hydride may also be added to increase adhesion, especially on polar substrates. Alternatively, polymeric and non-polymeric components may be combined with steps that include solution mixing (also known as a solvent mixture) or a combination. of fusion and dissolution methods. Solution mixing methods include, but are not limited to, multiple reactors in series, parallel or combinations thereof. Since the solution methods may sometimes result in better dispersion of the components, better efficacy of the second component is expected. Benefits may include using lesser amount of the second component to achieve comparable improvements in stretch resonance resistance while maintaining higher elastic properties such as reduced deformation and less hysteresis. Monolayer or multilayer elastic films and laminates comprising the composition of the invention may be prepared by any means including blown cell techniques, coextrusion, lamination and the like and combinations thereof. When the composition of the invention is used in multilayer constructions, the adjacent layered substrates of material may be polar or non-polar including, but not limited to, paper, metal, ceramic, glass and diverse polymer products, especially other polyolefins and combinations thereof. If a polymeric substrate is used, it can take a variety of forms, including but not limited to blankets, foams, fabrics, nonwovens, films, etc. Especially preferred laminates often comprise a selected nonwoven from the group consisting of blown, direct spinning blown fibers, carded cut fibers, spunbond fibers, and die cut fibers. The fabric may comprise two or more different decomposition fibers. For example, the fabric may comprise a very component polymeric fiber, wherein at least one of the polymeric components comprises at least a portion of the fiber surface.

Articles manufactured comprising the compositions of the invention may be selected from the group consisting of adult incontinence articles, hygiene articles, child care articles, surgeon's coats, operating room curtains, household cleaning articles, expandable food covers and personal care articles.

EXAMPLES OF SUITABLE COMPOSITIONS FOR ELASTIC ELAMINATED FILMS

Additional Examples 1-6 Continuous Solution Polymerization, Catalyst A1 / B2 + TENContinuous solution polymerizations are conducted in a well-mixed computerized reactor. Purified mixed alkane solvent (ISOPAR ™ E from ExxonMobilChemical Company), ethylene, 1-octene, and hydrogen (if used) are combined and fed to a 27 gallon reactor. Reactor feeds are measured by mass-flow controllers. Supply chain temperature is controlled by use of a glycol-cooled heat exchanger prior to normal intake. Catalyst component solutions are measured using pumps and mass flow meters. The reactor is operated full of liquid at a pressure of approximately 550 psig. Upon exiting the reactor, water and additives are injected into the polymer solution. The water hydrolyzes the catalysts, and completes the polymerization reactions. The post-reactor solution is then heated for preparation for a two-stage devolatization. The solvent and unreacted monomers are removed during the devolatization process. The polymer melt is pumped into a submerged pellet die.

Process details and results are contained in Table A. Table A - Suitable Compositions for Elastic Films and Laminates

<table> table see original document page 87 </column> </row> <table>

1 standard cm3 / min

2- [N- (2,6-di (1-methylethyl) phenyl) starch) (2-isopropylphenyl) (α-naphthalen-2-diyl) (6-pyridin-2-diyl) methane)] ammonium dimethyl

3 bis (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imino) zirconium dibenzyl

4 ppm in the final product calculated by mass balance.

5 polymer production rate

6 weight percent ethylene conversion in reactor

7 efficiency, kg polymer / g M where g M = g Hf + g Zr The resins made in Examples 13-39 through the process conditions of Table A were the ethylene-octene interpolymers and had TCrystaf, Tm-Crystaf (C), Areade Crystaf peak (% weight), density and 12 (g / 10 min) as shown in Table B below. Similarly, the amount of zinc: ethylene ratio of chain transfer agent used to prepare the polymers is shown.

Table B - Composition Properties of Examples for Elastic Film

<table> table see original document page 88 </column> </row> <table>

'*' denotes comparative example

Samples 1 *, 2 *, 3 *, 4 *, 5 *, 6 * and 8 * are ethylene alpha olefins

Sample 7 * is an SEBS styrene block copolymer. Compression Compression Molding of Examples 13-39 and 1 * 8 *

Compression molded films were prepared using the compositions of Examples 13-39 and 1-8 *. The films can be prepared by weighing the amount of polymer needed to fill a 9 inch by 6 inch wide and 0.1-0.5 mm mold. This polymer and mold were formed from the Mylar film and placed between chrome-coated metal foils and then the assembly was placed on a PW-L425 (City of Industry, California) laminate press pre-heated to 190 ° C for ethylene-based elastomers and 210 ° C for propylene based elastomers. The polymer is allowed to melt for 5 minutes under minimum pressure. Then a 10,000 pound force is applied for 5 minutes. Then the force is increased to 20,000 pounds, allowing one minute to pass. The set is then placed between 25 ° C water-cooled dishes and cooled for 5 minutes. The polymeric sheet is then removed from the mold and allowed to cure under ambient conditions (about 25 ° C) for at least 24 hours prior to testing for ethylene-based elastomers. The test specimens were extracted using a NAEF punch press.

Stress Relaxation Test 50 and 75%

For the measurement of stress relaxation, an Instron 5564 (Canton, Massachusetts) equipment fitted with lamination film retainers fitted with a 20 lb load cell fitted with an ambient chamber set at 37 ° C was used. After proper load cell calibration and heating, a 1 inch x 6 inch specimen is oriented parallel to the direction of travel of the crosshead and then secured with a 3 inch separation within the environmental chamber. After waiting at least 45 minutes for the temperature to equilibrate to 37 ° C, the sample was stretched to 50 or 75% strain at a rate of 51mm / min. The force was measured for 10 hours. For each deformation condition, a previously tested test piece was used.

Relaxation was quantified as (Fo-F) / Fo * 100% of shape Fo is the maximum force and F is the force as a function of time from 0 to 10 hours. 100% relaxation after 10 hours indicates complete loss of strength. 0% relaxation after 10 hours indicates no strength drop. Results are shown in Table C below.

100, 300, 500% Cycle Tests

For cycle testing, an Instron 5564 (Canton, Massachusetts) equipment equipped with pneumatic retainers and fitted with a 20 pound cell capacity is used. After proper load cell heating and calibration, an ASTMD1708 microtensile specimen was oriented parallel to the crosshead displacement direction and then secured with a separation of 22.25 mm. The measurement length is taken as 22.25mm. An untested sample was stretched to 100, 300, or 500% strain (Applied Effort) at a rate of 500% per minute (111.25 mm / min). The crosshead direction was immediately reversed and then returned to the initial tightening separation at 111.25 mm / min. The crosshead direction was reversed immediately to extend111.25 mm / min until a positive tensile force was measured. The effort corresponding to the onset of positive force was considered the immediate deformation. Recovery is defined as follows

Effort Applied (%) - Immediate Deformation (%)

Recovery (%) _ x 100

Applied Effort (%)

so that the 100% recovery corresponds to a sample that returned to its original length and a 0% recovery corresponds to a sample that was the same length as the maximum tightness separation during the test.

Effort measured as a percentage is defined as crosshead displacement divided by the initial grip separation of 22.25 mm and then multiplied by 100. Attention is defined as the force divided by the original cross-sectional area in the gauging section. Examples tested with the cycle at 100, 300 °.

Examples tested with 100, 3, 500, 500% cycle tests are shown in Table C.

Preferred compositions of the present invention often exhibit a recovery (%) of sugar with one or more of the following formulas shown in Figure 8:

<table> table see original document page 91 </column> </row> <table> Table C - Compression Molded Film Properties Prepared from the Example Compositions described above in Tables A and B

<table> table see original document page 92 </column> </row> <table>

* denotes comparative exampleof extruded film

Film processes exist in a variety of deforms. The present invention is compatible with many of them. Important parameters (ie melt index, additives, process aids, antioxidants, etc.) can be adjusted by those skilled in the art to accommodate the chosen method. For film examples, a Clawson extrusion coating line equipped with a 30 inch 30 L / D extruder powered by a 150 HP motor was used. The line had a 36 inchCloeren matrix. The matrix had a 24 inch border. Aperture was adjusted by 5-7 inches. COMPOSITIONS OF EXTRUDED FILM EXAMPLES WITHOUT LDPEA The compositions of Examples 21F, 22F, 36F, 21FL, 22FL, 36FL, 6FL *, 6F * were prepared using ethylene-octene copolymers similar to those described in the Tables. The eB. The densities and melt indices of the base resins and the corresponding extrusion conditions are shown in

Table D.

LDPE COMPOSITIONS

The compositions of Examples 21FL, 22FL and 6FL were prepared using ethylene octenosimilar copolymers as described in Tables A and B. The melts density and melting indexes of the base resins and the corresponding extrusion conditions are shown in Table D. The ethylene octene copolymers were then Blended dry with LDPE to form compositions comprising 94% ethylene octene copolymer and 6% LDPE. The dry mixture may be mixed (ie single screw extruder, double screw extruder, batch melt mixer, solvent mixture, etc.). For example, dry mixtures may be introduced into a preheated Haake set at 190 ° C and a rotor speed of 40 rpm. Once the torque has reached steady state (typically three to five minutes), the sample can be removed and allowed to cool. Alternatively, the dry mix may be introduced into a variety of extrusion and mixing equipment known in the art. The extrudate may be pelletized for later conversion or may be immediately converted to articles such as layer or layers in a film. The examples were prepared using dry blends, in-line blending and direct film conversion using the installation method described earlier in the "Extruded Film" section. <table> table see original document page 95 </column> </row> <table>

'F' denotes extruded film 'L' denotes presence of LDPER Stretch Resonance

The addition of LDPE can be used to improve resistance to stretch resonance which can improve line speed and film thickness uniformity. A critical aspect needed to describe stretch resonance (DR) consists of two fixed points anchoring over the fused blanket. Amatriz serves as one of the anchors. The pressure / cooling cylinder serves as the second anchor on the blanket. The flow from the matrix to the compression cylinder is stretched in planar extension. Stretch Ratio (DDR) is a dimensionless number describing the extent to which the film extends from the matrix to the cooling cylinder. The DDR is shown in the following equation:

(1) DDR = Vf / Vo

where: Vf = M / (hQ • Wf • ds) = Retraction Speed

Vo = M / (hQ • W0 • dm) = Matrix Output Speed

M = Mass Output Rate

Hx = Location Film Thickness x

Wx = In-Place Film Width x

dx = Density of polymer at local temperature x

By increasing the DDRc, higher line speeds can be allowed as used to produce the related examples. Higher line speed means higher productivity, generally desired in industrial fabrication processes.

Extruded Film Stress Relaxation Behavior

Specimens 1 inch wide by 6 inches long from the examples listed in Table D were cut to length parallel to the transverse direction (CD). CD is defined as the direction perpendicular to extrusion in the film plane. The specimens were extracted from areas of the film that were as uniform in thickness as possible. Typically, edges of the extruded film were avoided. The extruded films made from the example compositions were tested according to the stress relaxation method described above. The results are shown in Table E. For reference, the tensile relaxation performance of two commercial elastic laminate examples (9 * and 10 *) were included. <table> table see original document page 98 </column> </row> < table>

9 * and 10 * are examples of commercial elastic laminate. The other examples are films. Data show that the film examples of the invention may exhibit less relaxation compared to comparative examples. For example (see Figure 9), the 75% stress relaxation behavior of the films of the invention (examples 21F, 22F, 36F) exhibit menorelaxation compared to the random density and similar melt index ethylene-olefin copolymer (example 8F *) and commercial elastic laminates (examples 9 * and 10 *). In particular, (see Figure 10), comparison of the examples of the invention with LDPE (21FL, 22FL) and commercial examples (9F * to 9F *) also show reduced relaxation behavior at 50% deformation.

Claims (25)

1. Composition suitable for use in elastic films and laminates, characterized in that it comprises at least one ethylene / α-olefin interpolymer, and the interpolymer: (a) has a Mw / Mn of about 1.7 to 3.5 by minus one melting point, Tm / in degrees Celsius, and a density, d, in grams / cubic centimeter, where the numerical values of Tm and d correspond to the ratio: Tm> - 2002,9 + 4538,5 (d) - 2422, 2 (d) 2. (b) has a Mw / Mn of from about 1.7 to about 3.5, defined by a fusion heat, AH in J / g and a delta amount, AT, in degrees Celsius defined as the difference between the highest DSC peak and the highest CRYSTAF optic, where the numerical values of AT and AH have the following ratios: AT> -0.1299 (AH) + 62.81 for AH greater than zero and up to 130 J / g , AT> 48 ° C for HA greater than 130 J / g, where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer. , and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30Â ° C; or (c) is defined by an elastic recovery, Re, at 300 percent strain and 1 cycle measured with a compression molded film of the ethylene / α-olefin interpolymer, and having a density, d, in grams / centimeter where the Re ed numerical values satisfy the following relationship when the ethylene / α-olefin interpolymer is substantially free of a cross-linked phase: Re> 1481 - 1629 (d); or (d) has a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, with the fraction having a molar comonomer content at least 5 percent higher than that of a comparable random ethylene interpolymers fraction eluting between same temperatures, where said comparable random random ethylene interpolymer has the same comonomer (s) and a melt index, density and molar comonomer content (based on total polymer) in the range of 10 per cent of that of the ethylene interpolymer / α-olefin; or (e) has a storage module at 25 ° C, G "(25 ° C), and a storage module at 100 ° C, G '(100 ° C), where the G" (25 ° C) ratio is for G "(100 ° C) is in the range of about 1: 1 to about 9: 1; where the ethylene / α-olefin interpolymer has a density of about 0.85 to about 0.89 g / cc and a melt index (12) of from about 0.5g / 10 min to about -20g / 10 min. Composition according to Claim 1, characterized in that it further comprises about 12 percent by weight of the composition of a low pressure high density resin, ethylene vinyl acetate copolymer or a mixture thereof. Composition according to Claim 2, characterized in that it comprises from about 4 to about 8 weight percent of the composition of a low density high pressure resin. Composition according to Claim 3, characterized in that the ethylene / α-olefin interpolymer has a density of from about 0.86 to about-0.885 g / cc. Composition according to any one of Claims 1, 2 or 3, characterized in that the ethylene / α-olefin interpolymer has a melt index (12) of from about 0.75 g / 10 min to about 1, 5g / 10min Composition according to any one of Claims 1, 2 or 3, in the form of a melted cell layer, characterized in that the ethylene / α-olefin interpolymer has a melt index (12) of about 3 g / 10 min. about 17 g / 10 min. Composition according to any one of Claims 1, 2 or 3, in the form of an extruded delaminated layer, characterized in that the ethylene / α-olefin interpolymer has a melt index (12) of about 3 g / 10 min at about 17g / 10 mins Composition according to any one of Claims 1, 2 or 3, in the form of a blown film layer, characterized in that the ethylene / α-olefin interpolymer has a melt index (12) of about 0,5 g / 10. min at about 5g / l0 min. Composition according to any one of Claims 1, 2 or 3, characterized in that the ethylene / α-olefin interpolymer is made using a diethyl zinc chain transfer agent. Composition according to Claim 9, characterized in that the ethylene / α-olefin interpolymer is made using a concentration of diethyl zinc transfer agent such that the ratio of zinc to ethylene is about 0 ° C. 03 x 10 "3 to about 1.5 x 10" 3. Elastic film layer, characterized in that it comprises at least one ethylene / o-olefin interpolymer, where the interpolymer: (a) has a Mw / Mn of about 1.7 to 3.5, at least one melting point. , Tm, in degrees Celsius, and a density, d, in grams / cubic centimeter, where the numerical values of Tra ed correspond to the ratio: Tm - - 2002.9 + 4538.5 (d) - 2422.2 (d) 2. (b) has a Mw / Mn of from about 1.7 to about 3.5, defined by a fusion heat, AH in J / g and a delta amount, AT, in degrees Celsius defined as the temperature difference between highest DSC peak and higher CRYSTAF optic, where the numerical AT and AH values have the following ratios: AT> -0.1299 (AH) + 62.81 for AH greater than zero and up to 130 J / g, AT> 48 ° C for HA greater than 130 J / g, where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has a CRYSTAF peak identifiable, so the temperature of CRYSTAF is 30 ° C; or (c) is defined by an elastic recovery, Re, at 300 percent strain and 1 cycle measured with a compression molded film of the ethylene / α-olefin interpolymer, and having a density, d, in grams / centimeter where the Re ed numerical values satisfy the following relationship when the ethylene / o-olefin interpolymer is substantially free of a cross-linked phase: Re> 1481 - 1629 (d); or (d) has a molecular fraction eluting between 40 ° C and -130 ° C when fractionated using TREF, with the fraction having a molar comonomer content at least 5 percent higher than that of a comparable random ethylene interpolymers fraction. eluting between the same temperatures, where said comparable random random ethylene interpolymer has the same comonomer (s) and a melt index, density and molar comonomer content (based on total polymer) in the range of 10 per cent of that of the interpolymer ethylene / α-olefin; or (e) has a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° C, G "(100 ° C), where G' (25 ° C) ratio is for G "(100 ° C) is in the range of about 1: 1 to about 9: 1; where the ethylene / α-olefin interpolymer has a density of about 0.85 to about 0.89 g / cc and a melt index (12) of from about 0.5g / 10min to about -20g / lÕmin and the compression molded film layer is capable of stress relaxation from about 60% to 75% strain at 100%. ° F for at least 10 hours. Laminate, characterized in that it comprises at least one elastic or inelastic fabric and one elastic cell layer comprising at least one ethylene / olefin interpolymers, wherein the interpolymers: (a) have a Mw / Mn of about 1.7 to 3,5 at least one melting point Tm in degrees Celsius and a density d in grams / cubic centimeter, where the numerical values of Tm and d correspond to the ratio: Tm> - 2002,9 + 4538,5 (d) - 2422.2 (d) 2. (b) has a Mw / Mn of from about 1.7 to about 3.5, defined by a fusion heat, AH in J / g and a delta amount, AT, in degrees Celsius defined as the temperature difference between the highest DSC peak and the highest CRYSTAF optical where the numerical values of AT and AH have the following ratios: AT> -0.1299 (AH) + 62.81 for AH greater than zero and up to 130 J / g, AT> 48 ° C for HA greater than 130 J / g, where the CRYSTAF peak is determined to be at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30Â ° C; or (c) is defined by an elastic recovery, Re, at 300 percent strain and 1 cycle measured with a compression molded film of the ethylene / α-olefin interpolymer, and having a density, d, in grams / centimeter where the Re ed numerical values satisfy the following relationship when the ethylene / α-olefin interpolymer is substantially free of a cross-linked phase: Re> 1481 - 1629 (d); or (d) has a molecular fraction eluting between 40 ° C and 130 ° C when fractionated using TREF, with the fraction having a molar comonomer content at least 5 percent higher than that of a comparable random ethylene interpolymers fraction eluting between same temperatures, where said comparable random random ethylene interpolymer has the same comonomer (s) and a melt index, density and molar comonomer content (based on total polymer) in the range of 10 per cent of that of ethylene interpolymer Î ± -olefin; or (e) has a storage module at 25 ° C, G "(25 ° C), and a storage module at 100 ° C, G" (100 ° C), where the G "(25 ° C) ratio to G '(100 ° C) is in the range of about 1: 1 to about 9: 1, where the ethylene / α-olefin interpolymer has a density of about 0.85 to about 0.89 g / cc and an index melt (12) from about 0.5g / 10min to about -10g / 10min and the film layer is capable of stress-releasing at a maximum of 60% to 75% strain at 100 ° F per At least 10 hours. Laminate according to claim 12, characterized in that the film layer is capable of stress relaxation of about 40% to 75% strain at 100 ° F for at least 10 hours. Laminate according to claim 12, characterized in that the fabric is a nonwoven selected from the group consisting of blown, straight-spinning blown fibers, carded cut fibers, spunbond fibers, and airflow cut fibers. . Laminate according to Claim 12, characterized in that the fabric comprises at least two fibers of different composition. Laminate according to claim 12, characterized in that the fabric comprises a multicomponent fibrapolymer, wherein at least one of the polymeric components comprises at least a portion of the fiber surface. Manufactured article, characterized in that it comprises the composition as defined in claim 1, the elastic film layer as defined in claim 11, or the laminate as defined in claim 12. Manufactured article, characterized in that it comprises the composition as defined in claim 1, the elastic film layer as defined in claim 11, or the laminate as defined in claim 12 selected from the group consisting of adult incontinence articles, hygiene articles. women's clothing, child care articles, surgeon's lab coats, operating room curtains, household cleaning articles, expandable food covers and personal care articles. Elastic film layer according to Claim 11, characterized in that it is in the form of a multilayer film structure. Composition according to any one of Claims 1, 2 or 3, characterized in that it further comprises SEBS. Composition according to any one of Claims 1, 2 or 3, characterized in that the percentage recovery is greater than or equal to -1629 x density (g / cm3) + 1481. 22. Composition suitable for use on elastic laminated films, characterized in that it comprises at least one ethylene / o; -olefin interpolymer, wherein the interpolymer: (d) has a molecular fraction eluting between 40 ° C and 130 ° C when fractionated using TREF, where the fraction has a block index of at least 0.5 and deat is about 1 and a molecular weight distribution, Mw / Mn, greater than about 1.3; or (b) has an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw / Mn, greater than about 1.3, where the ethylene / α-olefin interpolymer has a density of about 0.85 to about 0.89 g / cc and a melt index of about 0.5g / 10 min to about 20g / 10min. Composition according to Claim 22, in the form of a molten film layer, characterized in that the ethylene / C-olefin interpolymer has a melt index (12) of from about 3g / 10 min to about 17g / 10 mins Composition according to Claim 22, in the form of an extruded laminate, characterized in that the ethylene / α-olefin interpolymer has a melt index (12) of from about 3 g / 10 min to about 17 g / 10 min. . Composition according to Claim 22, in the form of a blown film layer, characterized in that the ethylene / α-olefin interpolymer has a melt index (12) of from about 0.5g / 10 min to about 5g. / 10 mins